DE1493344B1 - Verfahren zur Herstellung von 16 alpha-Chlor- oder -Fluor-17(20)-pregnen-21-saeureestern und daraus erhaeltlichen 16 alpha-Chlor- oder -Fluor-17 alpha-hydroxy-20-keto-21-acyloxyverbindungen der Pregnanreihe - Google Patents
Verfahren zur Herstellung von 16 alpha-Chlor- oder -Fluor-17(20)-pregnen-21-saeureestern und daraus erhaeltlichen 16 alpha-Chlor- oder -Fluor-17 alpha-hydroxy-20-keto-21-acyloxyverbindungen der PregnanreiheInfo
- Publication number
- DE1493344B1 DE1493344B1 DE19641493344 DE1493344A DE1493344B1 DE 1493344 B1 DE1493344 B1 DE 1493344B1 DE 19641493344 DE19641493344 DE 19641493344 DE 1493344 A DE1493344 A DE 1493344A DE 1493344 B1 DE1493344 B1 DE 1493344B1
- Authority
- DE
- Germany
- Prior art keywords
- pregnen
- hydroxy
- chloro
- acetate
- 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.)
- Pending
Links
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- 238000005886 esterification reaction Methods 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- DVSJBCFGNHBBKG-UHFFFAOYSA-N 1,2,2-trichloro-n,n-diethylethenamine Chemical compound CCN(CC)C(Cl)=C(Cl)Cl DVSJBCFGNHBBKG-UHFFFAOYSA-N 0.000 claims description 5
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- 150000003839 salts Chemical class 0.000 claims description 5
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
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- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 3
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- 238000006640 acetylation reaction Methods 0.000 claims description 2
- 230000010933 acylation Effects 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- JWMFYGXQPXQEEM-WZBAXQLOSA-N pregnane Chemical class C1CC2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](CC)[C@@]1(C)CC2 JWMFYGXQPXQEEM-WZBAXQLOSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
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- 230000008018 melting Effects 0.000 description 74
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- 239000000047 product Substances 0.000 description 40
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- 239000002904 solvent Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 21
- 239000000706 filtrate Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
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- 239000000284 extract Substances 0.000 description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 8
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- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 1
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- IEBLCDMOEWJQAO-UHFFFAOYSA-N C(C)[AlH]CC.C(C)[Al](CC)CC Chemical compound C(C)[AlH]CC.C(C)[Al](CC)CC IEBLCDMOEWJQAO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- WZKSXHQDXQKIQJ-UHFFFAOYSA-N F[C](F)F Chemical compound F[C](F)F WZKSXHQDXQKIQJ-UHFFFAOYSA-N 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 239000003810 Jones reagent Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- PQGAHNJECSVDEI-UHFFFAOYSA-N [CH2]CCCCC Chemical compound [CH2]CCCCC PQGAHNJECSVDEI-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- VTHIKKVKIVQWHV-UHFFFAOYSA-N chromium(6+) oxygen(2-) pyridine Chemical compound [O-2].[O-2].[O-2].[Cr+6].C1=CC=NC=C1 VTHIKKVKIVQWHV-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010575 fractional recrystallization Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003862 glucocorticoid Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- KDCIHNCMPUBDKT-UHFFFAOYSA-N hexane;propan-2-one Chemical compound CC(C)=O.CCCCCC KDCIHNCMPUBDKT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229960001293 methylprednisolone acetate Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- BUGBHKTXTAQXES-OUBTZVSYSA-N selenium-80 Chemical compound [80Se] BUGBHKTXTAQXES-OUBTZVSYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940037128 systemic glucocorticoids Drugs 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J13/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having a carbon-to-carbon double bond from or to position 17
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05B—LOCKS; ACCESSORIES THEREFOR; HANDCUFFS
- E05B3/00—Fastening knobs or handles to lock or latch parts
- E05B3/02—Fastening knobs or handles to the spindle by pinning or riveting
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Steroid Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US329272A US3305546A (en) | 1963-12-09 | 1963-12-09 | Process for the production of 16-halo-17(20)-pregnenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1493344B1 true DE1493344B1 (de) | 1970-07-09 |
Family
ID=23284649
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19641493344 Pending DE1493344B1 (de) | 1963-12-09 | 1964-12-01 | Verfahren zur Herstellung von 16 alpha-Chlor- oder -Fluor-17(20)-pregnen-21-saeureestern und daraus erhaeltlichen 16 alpha-Chlor- oder -Fluor-17 alpha-hydroxy-20-keto-21-acyloxyverbindungen der Pregnanreihe |
| DE19641793599 Pending DE1793599A1 (de) | 1963-12-09 | 1964-12-01 | Verfahren zur Herstellung von 16ss-Hydroxy-,alpha-Chlor- und 16alpha-Fluor-17(20)-pregnen-21-saeureestern und mit diesen Verfahren herstellbare Verbindungen |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19641793599 Pending DE1793599A1 (de) | 1963-12-09 | 1964-12-01 | Verfahren zur Herstellung von 16ss-Hydroxy-,alpha-Chlor- und 16alpha-Fluor-17(20)-pregnen-21-saeureestern und mit diesen Verfahren herstellbare Verbindungen |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3305546A (enExample) |
| BE (1) | BE656870A (enExample) |
| DE (2) | DE1493344B1 (enExample) |
| FR (1) | FR1570405A (enExample) |
| GB (2) | GB1084467A (enExample) |
| IL (1) | IL22282A (enExample) |
| NL (3) | NL6414319A (enExample) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3364241A (en) * | 1966-07-29 | 1968-01-16 | Upjohn Co | Process for the production of 6alpha-fluoro-16alpha-halo pregnanes and the intermediates therefor |
| US3535348A (en) * | 1967-07-31 | 1970-10-20 | Upjohn Co | 3-oximes of 17(20)-en-21-oic acids of the pregnane series |
| US3539683A (en) * | 1967-07-31 | 1970-11-10 | Upjohn Co | Oral,parenteral and inhalation-therapy with 3,11-dioxo-4,17(20)-cis-pregnadien-21-oic acid,methyl ester,3-oxime |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB872032A (en) * | 1958-11-26 | 1961-07-05 | Upjohn Co | Improvements in or relating to steroids and the manufacture thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3056808A (en) * | 1961-10-09 | 1962-10-02 | Upjohn Co | 15beta-fluorinated corticosteroids |
| US3158625A (en) * | 1963-06-17 | 1964-11-24 | Syntex Corp | 20-(lower aliphatic hydrocarbon)-delta17(20)-pregnen-21-oic acids |
-
0
- BE BE656870D patent/BE656870A/xx unknown
- NL NL130311D patent/NL130311C/xx active
-
1963
- 1963-12-09 US US329272A patent/US3305546A/en not_active Expired - Lifetime
-
1964
- 1964-10-19 IL IL22282A patent/IL22282A/xx unknown
- 1964-11-11 GB GB45980/64A patent/GB1084467A/en not_active Expired
- 1964-11-11 GB GB13534/67A patent/GB1084468A/en not_active Expired
- 1964-12-01 DE DE19641493344 patent/DE1493344B1/de active Pending
- 1964-12-01 DE DE19641793599 patent/DE1793599A1/de active Pending
- 1964-12-08 FR FR1570405D patent/FR1570405A/fr not_active Expired
- 1964-12-09 NL NL6414319A patent/NL6414319A/xx unknown
-
1969
- 1969-08-19 NL NL6912579A patent/NL6912579A/xx unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB872032A (en) * | 1958-11-26 | 1961-07-05 | Upjohn Co | Improvements in or relating to steroids and the manufacture thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1793599A1 (de) | 1972-02-03 |
| NL6912579A (enExample) | 1969-11-25 |
| NL130311C (enExample) | |
| FR1570405A (enExample) | 1969-06-13 |
| IL22282A (en) | 1968-03-28 |
| NL6414319A (enExample) | 1965-06-10 |
| BE656870A (enExample) | |
| US3305546A (en) | 1967-02-21 |
| GB1084467A (en) | 1967-09-20 |
| GB1084468A (en) | 1967-09-20 |
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