IL42250A - 6alpha-methylprednisolone-21-metasulphobenzoate preparation process and pharmaceutical compositions - Google Patents
6alpha-methylprednisolone-21-metasulphobenzoate preparation process and pharmaceutical compositionsInfo
- Publication number
- IL42250A IL42250A IL42250A IL4225073A IL42250A IL 42250 A IL42250 A IL 42250A IL 42250 A IL42250 A IL 42250A IL 4225073 A IL4225073 A IL 4225073A IL 42250 A IL42250 A IL 42250A
- Authority
- IL
- Israel
- Prior art keywords
- formula
- product
- lithium
- methyl
- methylprednisolone
- Prior art date
Links
- 239000008194 pharmaceutical composition Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 3
- 150000003839 salts Chemical class 0.000 claims abstract 3
- QMWGSOMVXSRXQX-UHFFFAOYSA-N 3-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1 QMWGSOMVXSRXQX-UHFFFAOYSA-N 0.000 claims abstract 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical group [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- 229940102223 injectable solution Drugs 0.000 claims 2
- 150000002641 lithium Chemical group 0.000 claims 2
- VHRSUDSXCMQTMA-UHFFFAOYSA-N 11,17-dihydroxy-17-(2-hydroxyacetyl)-6,10,13-trimethyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthren-3-one Chemical compound CC12C=CC(=O)C=C1C(C)CC1C2C(O)CC2(C)C(O)(C(=O)CO)CCC21 VHRSUDSXCMQTMA-UHFFFAOYSA-N 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 1
- 229940096112 prednisol Drugs 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 2
- -1 alkali metal salts Chemical class 0.000 abstract description 2
- 239000003456 ion exchange resin Substances 0.000 abstract description 2
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 2
- VHRSUDSXCMQTMA-PJHHCJLFSA-N 6alpha-methylprednisolone Chemical compound C([C@@]12C)=CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2[C@@H](O)C[C@]2(C)[C@@](O)(C(=O)CO)CC[C@H]21 VHRSUDSXCMQTMA-PJHHCJLFSA-N 0.000 abstract 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003470 adrenal cortex hormone Substances 0.000 abstract 1
- 230000003110 anti-inflammatory effect Effects 0.000 abstract 1
- RKHQGWMMUURILY-UHRZLXHJSA-N cortivazol Chemical compound C([C@H]1[C@@H]2C[C@H]([C@]([C@@]2(C)C[C@H](O)[C@@H]1[C@@]1(C)C2)(O)C(=O)COC(C)=O)C)=C(C)C1=CC1=C2C=NN1C1=CC=CC=C1 RKHQGWMMUURILY-UHRZLXHJSA-N 0.000 abstract 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 abstract 1
- 230000000699 topical effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 206010001497 Agitation Diseases 0.000 description 3
- 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 3
- 238000013019 agitation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000025747 Rheumatic disease Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002917 arthritic effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940112482 entsol Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960004584 methylprednisolone Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960005205 prednisolone Drugs 0.000 description 1
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 description 1
- 230000000552 rheumatic effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2004—Excipients; Inactive ingredients
- A61K9/2009—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J31/00—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
- A61K31/57—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane or progesterone
- A61K31/573—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane or progesterone substituted in position 21, e.g. cortisone, dexamethasone, prednisone or aldosterone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2004—Excipients; Inactive ingredients
- A61K9/2022—Organic macromolecular compounds
- A61K9/205—Polysaccharides, e.g. alginate, gums; Cyclodextrin
- A61K9/2054—Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Steroid Compounds (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
1375357 Corticoid 21-sulphobenzoate ROUSSEL UCLAF 21 May 1973 [19 May 1972] 24013/73 Heading C2U The invention comprises 6α-methylprednisolone 21-(m-sulphobenzoate) and its alkali metal salts. The salts are prepared from the corresponding 21-methanesulphonate by reaction with a di-(alkali metal) m-sulphobenzoate in the presence of an N-alkyl-amide (e.g. DMF), and may be converted to the free acid by passing over an acidic ion-exchange resin. The free acid may thereafter be resalified. 6α-Methylprednisolone 21-methanesulphonate is prepared from the free 21-ol by reaction with mesyl chloride. Antiinflammatory compositions for oral, parenteral, topical and rectal administration comprise a compound of the invention and a carrier.
[GB1375357A]
Description
NEW 6 PREPARATION PROCESS AND PHARMACEUTICAL COMPOSITIONS 21 The present invention has as object the novel methylprednisolone compound according to formula CH3 wherein 6 The invention also has as object a process for preparing the derivative defined by formula which consists of reacting a functional derivati e of phonic acid with so as to obtain the product of formula 3 the said process being characterized in that one reacts the product of formula II thus obtained with an acid dialkaline in the presence of an amide and that one isolates the product of formula I thus obtained in which represents an metal other than lithium which one passes an ion exchange used in acid form so as to obtain a compound of formula I containing instead of lithium a hydrogen atom and one reacts this latter product with lithium hydroxide or carbonate so as to obtain the product wherei n M desi gnates l of formula In putting into effect the process for preparing the derivatives of formula I described one preferably operates as One dissolves 6 a in one cools to a temperature of about and one adds One heats at reflux for a few minutes and one collects prednisolone heats the 6 with metasulphobenzoic acid disodium salt in the presence of a amide such as dimethyl One collects One suspends the 6 a sulphobenzoate in one adds an ion exchange resin used in acid One collects the filtrate containing the product of formula I in which M represents a hydrogen isolates this latter product if or alkalizes the filtrate using an hydroxide and collects the product of formula I in which represents l es The of formula I very interesting more specifically Because of these remarkable properties the of formula I i s very useful in human more in the treatment of inflammatory manifestations of rheumatic or arthritic The usual variable according to the product the subject treated and the infirmity can be for example from 2 to 100 per by injectable route in a In Israel Patent 12387 in 3089881 and in certai n British Patent 1103 686 there described and especially the sodium of compounds similar to those of the present The lithium salt is not described in any of The lithium salt is characterized by a substantially greater solubility in water 8 per compared with that of the sodium salt per the solutions of the lithium salt have a good stability and this is an import property as regards pharmaceutical compositions of The invention has moreover as object the pharmaceutical i ngredi ent sol compositions containing as active ul phobenzoate of formula I and more specifically the injectable aqueous These pharmaceutical compositions are effected in such a way that they can be administered by parenteral or local They can be solids or liquids and can take the currently used pharmaceutic i 21 Stage A sodium One heats to under agitations a mixture of 6 o monosodium e and 6 of adds of sodium then 160 of dimethylformamide and distills under agitation till boiling point remains constant at 151 cine cools the suspension to under en atmosphere of nitrogen adds 10 of agitates for 5 hours at one evaporates to dryness un up the residue with of ethanol and evaporates to dryness under One makes the residue into a paste in a heated state in 60 ml of ethyl acetate and takes to reflux for 10 One washes the residue with ethyl acetate and dries vacuums the sodium salt is once again from After drying under vacuum at then at ambient on obtains of in the form of colourless acid form and agitates for one pours the solution on to 65 of activated Dowex 0 resin acid collects the pH 1 to liquid and one adds I o aqueous solution of lithium hydroxide to the acid phase obtained under and evaporates to one suspends the residue in 10 of admixed with 25 of water and heats unde agitation one the temperature back to brings the limpid filtrate to and initiates One leaves the mixture to stand for one night at then for one hour at and the precipitate is washed with dried under vacuum then in an oven at and finally insufficientOCRQuality
Claims (2)
1. 42250/2 WHAT IS CLAIMED IS: 1 ) The 6a -methylprednlsolone derivatives of formula I: in which M represents a lithium atom.
2. ) Process for preparing the derivatives defined by formula I of Claim 1 ) , which consists of reading a functional derivative of methanesul phonic add with 6 a -methyl prednisolone so as to obtain the product of formula II II / 1 the said process being characterized In that one reacts the product of formula II thus obtained with an m-sulphobenzoic add dlalkallne salt in the presence of a dialkyl amide and that eit er one isolates the product of formula I thus obtained in whi ch M represents an alkali - metal atom, one passes the said product of formula I over an 1on exchange resin, used in add form, so as to obtain the product of formula I in whi ch M represents a hydrogen atom, and that one reacts this latter product with a lithium hydroxide or a lithium carbonate so as to obtain the product of formula I in which M represents a lithium atom. 42250/3 3) Process according to Claim 2), characterized in that the m-sulphobenzoic acid dialkaline salt is disodium salt, and that the dialkylamide is dimethyl formamide and that the alkali-metal hydroxide is lithium hydroxide. 4) A pharmaceutical composition containing as acti e i ngredient βα-methyl predni sol one-21 - 1 i thi um-metas ul phobenzoate . 5) An aqueous injectable solution, containing 6 -methyl-prednisolone-21-1 ithi um-metasul phobenzoate. 6) An aqueous injectable solution containing 6a-methyl-predinisolone-21-lithium-metasulphobenzoate, propylene glycol and lith um benzoate. P.O.Box 33116 Attorneys for Applicant
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7218035A FR2193576B1 (en) | 1972-05-19 | 1972-05-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL42250A0 IL42250A0 (en) | 1973-07-30 |
| IL42250A true IL42250A (en) | 1977-06-30 |
Family
ID=9098837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL42250A IL42250A (en) | 1972-05-19 | 1973-05-11 | 6alpha-methylprednisolone-21-metasulphobenzoate preparation process and pharmaceutical compositions |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS5212777B2 (en) |
| AT (1) | AT325221B (en) |
| AU (1) | AU473292B2 (en) |
| BE (1) | BE799615A (en) |
| CA (1) | CA977746A (en) |
| CH (1) | CH572068A5 (en) |
| CS (1) | CS165956B2 (en) |
| DD (1) | DD104787A5 (en) |
| DK (1) | DK133683B (en) |
| EG (1) | EG11080A (en) |
| ES (1) | ES414870A1 (en) |
| FI (1) | FI52588C (en) |
| FR (1) | FR2193576B1 (en) |
| GB (1) | GB1375357A (en) |
| HU (1) | HU165993B (en) |
| IE (1) | IE37657B1 (en) |
| IL (1) | IL42250A (en) |
| NL (1) | NL7306962A (en) |
| NO (1) | NO138148C (en) |
| PH (1) | PH12351A (en) |
| PL (1) | PL85506B1 (en) |
| SE (1) | SE399711B (en) |
| SU (1) | SU493961A3 (en) |
| YU (1) | YU35037B (en) |
| ZA (1) | ZA733340B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5112816A (en) * | 1975-04-03 | 1976-01-31 | Wakao Kanao | TAIRUBARIPUREKYASUTOKONKURIITONO SEIZOHOHO |
| JPS51122118A (en) * | 1975-04-15 | 1976-10-26 | Wakao Kanao | Production of tiled precast concrete |
| US4588718A (en) * | 1984-03-28 | 1986-05-13 | The Upjohn Company | Carboxy containing ester prodrugs of corticosteroids |
| US4948533A (en) * | 1984-03-28 | 1990-08-14 | The Upjohn Company | 11a-hydroxy steroid diester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3089881A (en) * | 1957-10-29 | 1963-05-14 | Schering Corp | Sulfocarboxylic acid esters of hydroxylated steroids |
-
1972
- 1972-05-19 FR FR7218035A patent/FR2193576B1/fr not_active Expired
-
1973
- 1973-05-04 CH CH638173A patent/CH572068A5/xx not_active IP Right Cessation
- 1973-05-10 PH PH7314601A patent/PH12351A/en unknown
- 1973-05-11 IL IL42250A patent/IL42250A/en unknown
- 1973-05-15 YU YU1278/73A patent/YU35037B/en unknown
- 1973-05-15 FI FI731564A patent/FI52588C/en active
- 1973-05-15 CS CS3446A patent/CS165956B2/cs unknown
- 1973-05-16 BE BE131184A patent/BE799615A/en unknown
- 1973-05-17 SE SE7306996A patent/SE399711B/en unknown
- 1973-05-17 ZA ZA733340A patent/ZA733340B/en unknown
- 1973-05-17 HU HURO730A patent/HU165993B/hu unknown
- 1973-05-17 PL PL1973162627A patent/PL85506B1/pl unknown
- 1973-05-18 NL NL7306962A patent/NL7306962A/xx unknown
- 1973-05-18 DD DD170919A patent/DD104787A5/xx unknown
- 1973-05-18 NO NO2058/73A patent/NO138148C/en unknown
- 1973-05-18 ES ES414870A patent/ES414870A1/en not_active Expired
- 1973-05-18 CA CA171,864A patent/CA977746A/en not_active Expired
- 1973-05-18 JP JP48054774A patent/JPS5212777B2/ja not_active Expired
- 1973-05-18 SU SU1916475A patent/SU493961A3/en active
- 1973-05-18 AU AU55900/73A patent/AU473292B2/en not_active Expired
- 1973-05-19 EG EG186/73A patent/EG11080A/en active
- 1973-05-21 GB GB2401373A patent/GB1375357A/en not_active Expired
- 1973-05-21 AT AT441473A patent/AT325221B/en not_active IP Right Cessation
- 1973-05-21 IE IE811/73A patent/IE37657B1/en unknown
- 1973-05-21 DK DK277473AA patent/DK133683B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1375357A (en) | 1974-11-27 |
| YU35037B (en) | 1980-06-30 |
| AU5590073A (en) | 1974-11-21 |
| NO138148C (en) | 1978-07-12 |
| NO138148B (en) | 1978-04-03 |
| IE37657L (en) | 1973-11-19 |
| CA977746A (en) | 1975-11-11 |
| DE2325358B2 (en) | 1976-01-29 |
| AU473292B2 (en) | 1976-06-17 |
| NL7306962A (en) | 1973-11-21 |
| CH572068A5 (en) | 1976-01-30 |
| IE37657B1 (en) | 1977-09-14 |
| FR2193576B1 (en) | 1975-08-08 |
| DK133683C (en) | 1976-11-15 |
| FI52588C (en) | 1977-10-10 |
| FR2193576A1 (en) | 1974-02-22 |
| ES414870A1 (en) | 1976-05-01 |
| SE399711B (en) | 1978-02-27 |
| DK133683B (en) | 1976-06-28 |
| PH12351A (en) | 1979-01-29 |
| PL85506B1 (en) | 1976-04-30 |
| ZA733340B (en) | 1974-11-27 |
| EG11080A (en) | 1977-04-30 |
| FI52588B (en) | 1977-06-30 |
| SU493961A3 (en) | 1975-11-28 |
| IL42250A0 (en) | 1973-07-30 |
| HU165993B (en) | 1974-12-28 |
| CS165956B2 (en) | 1975-12-22 |
| DD104787A5 (en) | 1974-03-20 |
| AT325221B (en) | 1975-10-10 |
| JPS4948653A (en) | 1974-05-11 |
| JPS5212777B2 (en) | 1977-04-09 |
| YU127873A (en) | 1979-12-31 |
| BE799615A (en) | 1973-11-16 |
| DE2325358A1 (en) | 1973-11-29 |
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