CA2127272A1 - Halogenation using halo-vilsmeier reagent - Google Patents

Halogenation using halo-vilsmeier reagent

Info

Publication number: CA2127272A1
Authority: CA; Canada
Prior art keywords: reagent; process according; vilsmeier reagent; halogen; chloride
Prior art date: 1992-01-06
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.): Abandoned

Application number

CA002127272A

Other languages

English (en)

French (fr)

Inventor

Neil Howard Baine

Donald Nathaniel Klein

Richard Eric Mewshaw

Franklin Fell Owings

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

SmithKline Beecham Corp

Original Assignee

Individual

Priority date (The priority date 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 date listed.)

1992-01-06

Filing date

1993-01-06

Publication date

1993-07-22

1993-01-06 Application filed by Individual filed Critical Individual

1993-07-22 Publication of CA2127272A1 publication Critical patent/CA2127272A1/en

Status Abandoned legal-status Critical Current

Links

230000026030 halogenation Effects 0.000 title claims description 7
238000005658 halogenation reaction Methods 0.000 title claims description 7
238000000034 method Methods 0.000 claims abstract description 42
230000003637 steroidlike Effects 0.000 claims abstract description 20
238000002360 preparation method Methods 0.000 claims abstract description 8
YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
239000003153 chemical reaction reagent Substances 0.000 claims description 35
150000001875 compounds Chemical class 0.000 claims description 25
CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 18
ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 14
CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 14
239000002904 solvent Substances 0.000 claims description 13
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 8
239000002253 acid Substances 0.000 claims description 8
239000007789 gas Substances 0.000 claims description 8
IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
150000003948 formamides Chemical class 0.000 claims description 7
229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
150000003839 salts Chemical class 0.000 claims description 7
XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
150000002576 ketones Chemical class 0.000 claims description 6
239000012453 solvate Substances 0.000 claims description 6
125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
230000008878 coupling Effects 0.000 claims description 5
238000010168 coupling process Methods 0.000 claims description 5
238000005859 coupling reaction Methods 0.000 claims description 5
YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 claims description 5
229910052757 nitrogen Inorganic materials 0.000 claims description 5
150000001408 amides Chemical class 0.000 claims description 4
229910052794 bromium Inorganic materials 0.000 claims description 4
XIXYNENNFUBWFK-UHFFFAOYSA-M bromomethylidene(dimethyl)azanium;bromide Chemical group [Br-].C[N+](C)=CBr XIXYNENNFUBWFK-UHFFFAOYSA-M 0.000 claims description 4
229910052740 iodine Inorganic materials 0.000 claims description 4
WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical group [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 4
125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 3
ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
-1 alkyl lithium Chemical compound 0.000 claims description 3
GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
150000002148 esters Chemical class 0.000 claims description 3
125000000524 functional group Chemical group 0.000 claims description 3
229910052736 halogen Inorganic materials 0.000 claims description 3
150000002367 halogens Chemical class 0.000 claims description 3
125000005842 heteroatom Chemical group 0.000 claims description 3
239000001257 hydrogen Substances 0.000 claims description 3
229910052739 hydrogen Inorganic materials 0.000 claims description 3
125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
239000011630 iodine Substances 0.000 claims description 3
229910052744 lithium Inorganic materials 0.000 claims description 3
229910052751 metal Inorganic materials 0.000 claims description 3
239000002184 metal Substances 0.000 claims description 3
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
238000010791 quenching Methods 0.000 claims description 3
230000000171 quenching effect Effects 0.000 claims description 3
229920006395 saturated elastomer Polymers 0.000 claims description 3
125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
229910006069 SO3H Inorganic materials 0.000 claims description 2
150000004703 alkoxides Chemical class 0.000 claims description 2
150000003857 carboxamides Chemical group 0.000 claims description 2
230000005595 deprotonation Effects 0.000 claims description 2
238000010537 deprotonation reaction Methods 0.000 claims description 2
150000004795 grignard reagents Chemical class 0.000 claims description 2
FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical group [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 2
238000011065 in-situ storage Methods 0.000 claims 5
125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 2
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
239000001301 oxygen Substances 0.000 claims 2
229910052760 oxygen Inorganic materials 0.000 claims 2
150000004678 hydrides Chemical class 0.000 claims 1
238000006243 chemical reaction Methods 0.000 abstract description 7
150000001993 dienes Chemical class 0.000 abstract description 4
125000001475 halogen functional group Chemical group 0.000 abstract description 2
238000002955 isolation Methods 0.000 abstract description 2
230000009466 transformation Effects 0.000 abstract description 2
239000007858 starting material Substances 0.000 abstract 1
XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
239000000243 solution Substances 0.000 description 18
239000012074 organic phase Substances 0.000 description 11
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
239000000725 suspension Substances 0.000 description 8
239000000203 mixture Substances 0.000 description 7
BTOJSYRZQZOMOK-UHFFFAOYSA-N 4-chloro-7-(4-methylphenyl)sulfonylpyrrolo[2,3-d]pyrimidine Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N1C2=NC=NC(Cl)=C2C=C1 BTOJSYRZQZOMOK-UHFFFAOYSA-N 0.000 description 6
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
125000000217 alkyl group Chemical group 0.000 description 5
239000000047 product Substances 0.000 description 5
YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 5
YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
239000011541 reaction mixture Substances 0.000 description 4
239000007787 solid Substances 0.000 description 4
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
239000008346 aqueous phase Substances 0.000 description 3
239000000706 filtrate Substances 0.000 description 3
238000001914 filtration Methods 0.000 description 3
239000012299 nitrogen atmosphere Substances 0.000 description 3
238000003756 stirring Methods 0.000 description 3
HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
125000003118 aryl group Chemical group 0.000 description 2
230000015572 biosynthetic process Effects 0.000 description 2
239000012267 brine Substances 0.000 description 2
239000001569 carbon dioxide Substances 0.000 description 2
229910002092 carbon dioxide Inorganic materials 0.000 description 2
238000006073 displacement reaction Methods 0.000 description 2
150000004820 halides Chemical class 0.000 description 2
150000002430 hydrocarbons Chemical group 0.000 description 2
239000000543 intermediate Substances 0.000 description 2
150000002500 ions Chemical class 0.000 description 2
238000004519 manufacturing process Methods 0.000 description 2
239000002244 precipitate Substances 0.000 description 2
125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
150000003431 steroids Chemical class 0.000 description 2
VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
238000005292 vacuum distillation Methods 0.000 description 2
VWYOARFPMUBYFG-ZTPZMMAUSA-N (8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylhept-6-en-2-yl]-1,2,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-3-one Chemical compound C1CC2CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@@H](CCCC(C)=C)C)[C@@]1(C)CC2 VWYOARFPMUBYFG-ZTPZMMAUSA-N 0.000 description 1
ZYEAZCNZFTUVNG-GYKMGIIDSA-N (8s,9s,10r,13r,14s,17r)-3-bromo-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,7,8,9,11,12,14,15,16,17-decahydro-1h-cyclopenta[a]phenanthrene Chemical compound C1C=C2C=C(Br)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 ZYEAZCNZFTUVNG-GYKMGIIDSA-N 0.000 description 1
AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
239000005977 Ethylene Substances 0.000 description 1
WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
BQCGLFCQDOUJOH-UHFFFAOYSA-N [C].C(C)OCC Chemical compound [C].C(C)OCC BQCGLFCQDOUJOH-UHFFFAOYSA-N 0.000 description 1
150000007513 acids Chemical class 0.000 description 1
150000001347 alkyl bromides Chemical class 0.000 description 1
230000009435 amidation Effects 0.000 description 1
238000007112 amidation reaction Methods 0.000 description 1
239000007900 aqueous suspension Substances 0.000 description 1
125000003710 aryl alkyl group Chemical group 0.000 description 1
230000031709 bromination Effects 0.000 description 1
238000005893 bromination reaction Methods 0.000 description 1
125000001246 bromo group Chemical group Br* 0.000 description 1
229910052799 carbon Inorganic materials 0.000 description 1
125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
230000021523 carboxylation Effects 0.000 description 1
238000006473 carboxylation reaction Methods 0.000 description 1
150000001735 carboxylic acids Chemical class 0.000 description 1
230000003197 catalytic effect Effects 0.000 description 1
150000001805 chlorine compounds Chemical class 0.000 description 1
FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical class ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
125000001309 chloro group Chemical group Cl* 0.000 description 1
QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 1
RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
238000006251 dihalogenation reaction Methods 0.000 description 1
238000004821 distillation Methods 0.000 description 1
125000000623 heterocyclic group Chemical group 0.000 description 1
150000004677 hydrates Chemical class 0.000 description 1
230000002401 inhibitory effect Effects 0.000 description 1
239000007788 liquid Substances 0.000 description 1
229910052749 magnesium Inorganic materials 0.000 description 1
239000011777 magnesium Substances 0.000 description 1
229910052943 magnesium sulfate Inorganic materials 0.000 description 1
235000019341 magnesium sulphate Nutrition 0.000 description 1
230000001404 mediated effect Effects 0.000 description 1
229910052987 metal hydride Inorganic materials 0.000 description 1
150000004681 metal hydrides Chemical class 0.000 description 1
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
230000000269 nucleophilic effect Effects 0.000 description 1
239000012434 nucleophilic reagent Substances 0.000 description 1
150000007524 organic acids Chemical class 0.000 description 1
235000005985 organic acids Nutrition 0.000 description 1
239000003960 organic solvent Substances 0.000 description 1
125000003431 oxalo group Chemical group 0.000 description 1
230000009257 reactivity Effects 0.000 description 1
238000010898 silica gel chromatography Methods 0.000 description 1
239000012265 solid product Substances 0.000 description 1
125000001424 substituent group Chemical group 0.000 description 1
125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
231100000331 toxic Toxicity 0.000 description 1
230000002588 toxic effect Effects 0.000 description 1
238000000844 transformation Methods 0.000 description 1
238000001665 trituration Methods 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J3/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
- C07J3/005—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom the carbon atom being part of a carboxylic function
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
- C07J41/0033—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005
- C07J41/0066—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 the 17-beta position being substituted by a carbon atom forming part of an amide group

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Health & Medical Sciences (AREA)
General Health & Medical Sciences (AREA)
Steroid Compounds (AREA)
Nitrogen Condensed Heterocyclic Rings (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

CA002127272A 1992-01-06 1993-01-06 Halogenation using halo-vilsmeier reagent Abandoned CA2127272A1 (en)

Applications Claiming Priority (4)

Application Number	Priority Date	Filing Date
US81717992A	1992-01-06	1992-01-06
US07/817,179		1992-01-06
US94134892A	1992-09-04	1992-09-04
US07/941,348		1992-09-04

Publications (1)

Publication Number	Publication Date
CA2127272A1 true CA2127272A1 (en)	1993-07-22

Family

ID=27124147

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CA002127272A Abandoned CA2127272A1 (en)	1992-01-06	1993-01-06	Halogenation using halo-vilsmeier reagent

Country Status (23)

Country	Link
EP (1)	EP0643723A4 (hu)
JP (1)	JPH07505138A (hu)
KR (1)	KR940703849A (hu)
CN (1)	CN1077201A (hu)
AP (1)	AP370A (hu)
AU (1)	AU666167B2 (hu)
BG (1)	BG98887A (hu)
BR (1)	BR9305786A (hu)
CA (1)	CA2127272A1 (hu)
CZ (1)	CZ161994A3 (hu)
FI (1)	FI943214A0 (hu)
HU (1)	HUT68273A (hu)
IL (1)	IL104302A (hu)
MA (1)	MA22761A1 (hu)
MX (1)	MX9300025A (hu)
NO (1)	NO942535D0 (hu)
NZ (1)	NZ246788A (hu)
OA (1)	OA09961A (hu)
RU (1)	RU94038223A (hu)
SI (1)	SI9300006A (hu)
SK (1)	SK80094A3 (hu)
TW (1)	TW300226B (hu)
WO (1)	WO1993014106A1 (hu)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US5641765A (en) *	1992-11-18	1997-06-24	Smithkline Beecham Corporation	17-αand 17-βsubstituted acyl-3-carboxy-3,5-dienes and use in inhibiting 5-α-reductase
US5683995A (en) *	1992-11-18	1997-11-04	Smithkline Beecham Corporation	17 substituted acyl-3-carboxy 3,5-diene steroidals as α-reductase inhibitors
EA012414B1 (ru)	2004-06-08	2009-10-30	Темпл Юниверсити Оф Дзе Коммонвелт Систем Оф Хайер Эдьюкейшн	Гетероарилсульфоны и сульфонамиды и их терапевтические применения

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
ZA883034B (en) *	1987-04-29	1989-03-29	Smithkline Beckman Corp	Steroid 5-alpha-reductase inhibitors

1993
- 1993-01-04 IL IL104302A patent/IL104302A/en not_active IP Right Cessation
- 1993-01-05 MA MA23050A patent/MA22761A1/fr unknown
- 1993-01-05 AP APAP/P/1993/000473A patent/AP370A/en active
- 1993-01-06 BR BR9305786A patent/BR9305786A/pt not_active Application Discontinuation
- 1993-01-06 HU HU9402030A patent/HUT68273A/hu unknown
- 1993-01-06 CN CN93101175A patent/CN1077201A/zh active Pending
- 1993-01-06 WO PCT/US1993/000079 patent/WO1993014106A1/en not_active Application Discontinuation
- 1993-01-06 KR KR1019940702343A patent/KR940703849A/ko not_active Application Discontinuation
- 1993-01-06 AU AU34348/93A patent/AU666167B2/en not_active Ceased
- 1993-01-06 SK SK800-94A patent/SK80094A3/sk unknown
- 1993-01-06 RU RU94038223/04A patent/RU94038223A/ru unknown
- 1993-01-06 JP JP5512542A patent/JPH07505138A/ja active Pending
- 1993-01-06 EP EP93902957A patent/EP0643723A4/en not_active Ceased
- 1993-01-06 CA CA002127272A patent/CA2127272A1/en not_active Abandoned
- 1993-01-06 SI SI19939300006A patent/SI9300006A/sl unknown
- 1993-01-06 MX MX9300025A patent/MX9300025A/es unknown
- 1993-01-06 CZ CZ941619A patent/CZ161994A3/cs unknown
- 1993-01-06 NZ NZ246788A patent/NZ246788A/en unknown
- 1993-01-29 TW TW082100552A patent/TW300226B/zh active
1994
- 1994-07-04 OA OA60533A patent/OA09961A/en unknown
- 1994-07-05 NO NO942535A patent/NO942535D0/no unknown
- 1994-07-05 FI FI943214A patent/FI943214A0/fi unknown
- 1994-07-05 BG BG98887A patent/BG98887A/bg unknown

Also Published As

Publication number	Publication date
MX9300025A (es)	1994-01-31
TW300226B (hu)	1997-03-11
CZ161994A3 (en)	1995-03-15
CN1077201A (zh)	1993-10-13
AP9300473A0 (en)	1993-01-31
AP370A (en)	1994-11-10
KR940703849A (ko)	1994-12-12
EP0643723A4 (en)	1995-05-10
HUT68273A (en)	1995-06-28
AU666167B2 (en)	1996-02-01
HU9402030D0 (en)	1994-09-28
JPH07505138A (ja)	1995-06-08
IL104302A (en)	1998-02-22
NO942535L (no)	1994-07-05
BG98887A (bg)	1995-05-31
AU3434893A (en)	1993-08-03
FI943214L (fi)	1994-07-05
OA09961A (en)	1995-12-11
WO1993014106A1 (en)	1993-07-22
NZ246788A (en)	1996-11-26
BR9305786A (pt)	1997-02-18
SK80094A3 (en)	1994-12-07
IL104302A0 (en)	1993-05-13
EP0643723A1 (en)	1995-03-22
SI9300006A (en)	1993-09-30
NO942535D0 (no)	1994-07-05
RU94038223A (ru)	1997-04-20
FI943214A0 (fi)	1994-07-05
MA22761A1 (fr)	1993-10-01

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