IL30956A - 13beta-n-propyl-des-a-gonatrien-5-ols and process for preparing same - Google Patents
13beta-n-propyl-des-a-gonatrien-5-ols and process for preparing sameInfo
- Publication number
- IL30956A IL30956A IL3095665A IL3095665A IL30956A IL 30956 A IL30956 A IL 30956A IL 3095665 A IL3095665 A IL 3095665A IL 3095665 A IL3095665 A IL 3095665A IL 30956 A IL30956 A IL 30956A
- Authority
- IL
- Israel
- Prior art keywords
- organic carboxylic
- carboxylic acid
- acid
- carbon
- formula
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000000887 hydrating effect Effects 0.000 claims description 2
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical group [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002730 mercury Chemical class 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 2
- 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 claims 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 239000003456 ion exchange resin Substances 0.000 claims 1
- 229920003303 ion-exchange polymer Polymers 0.000 claims 1
- 229940124530 sulfonamide Drugs 0.000 claims 1
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 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 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- -1 sulfonic acid monohydrate Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
-
- 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
13 PROCESS FOB SAME 5 1 out of 23183 Pile 13036 T where X and Y represen the suhstituents where Ac designates an acyl radical or an organic carboxylic acid having 2 to 7 carbon or and Y together represent an oxygen atom and to a process for preparing these The compounds of the present invention are of value in steroid synthesis and especially in the synthesis of compounds described and claimed in the copending patent application from which the present application has been divided The novel compounds according to the present invention are obtained by the process which comprises the steps 5 7 9 reacting with an oxidizing if desired ethynylating the resulting by the action of an esterifying derivative of an organic carboxylic acid having from 2 to 7 carbon desired hydrating the ethynyl function of the ester of the formula wherein Ac represents the acyl of an organic carboxylic acid having from to 7 carbon by the action of water in the presence of a hydration According to the invention there are obtained the novel gonatr An ester CH out o 23183 File 13036 carboxylic wherein Ac represents the acyl of an organic carboxylic acid having to 7 carbon The process summarized by the flow diagram the of 13036 68 represents the of an organic carboxylic acid having from 2 to 7 carbon Shis process is essentially characterized in that 5 7 is subjected to the action of an oxidizing agent under the usual conditons to oxidize the hydroxy group to a An ethynylating agent is reacted with the resultant 7 9 thus obtainin This latter compound esterifled the aid of a functiona derivative of an organic carboxylic acid havin from 2 to 7 carbon atoms to give a 5 79 Δ The ethynyl function of this ester is catalytically hydrated to give a 5 7 The performance of the process of invention may be characterized advantageously by the following The oxidizing agent utilized to oxidize the 5 79 group of into the 17 is preferably chromic acid and the reaction is conducted in the presence of sulfuric acid in an acetonic media The ethynylating which is allowed upo the can be any ethynylating agent conventionally used to ethynylate a 17 ketone however it preferable out of 13036 g Is esterifled by means of a functional such as an acid chloride an of an organic carboxylic acid having from 2 to 7 carbon When the reaction conducted with acetic acid it is preferable to conduct the same in the presence of a strongly acidic such as oluene sulfonic She ethynyl function of the 5 79 acyloxy is hydrated according to conventional methods in steroid Preferably the reaction is conducted in a dilute in the presence of a hydration such as a mercury salt of or an ion exchange resi containing mercuric The following example illustrates the It is to be that it presents no limiting EXAMPLE 5 Step A solution of 24 gm of 5 Δ in 480 cc pure acetone was cooled and within a space of 5 minutes the following solution was Chromic acid gm Water cc out of 23183 Pile 13036 mixture was further agitated for another 15 then poured into of The a mixture was extracted with methylene The extracts were with an aqueous saturated solution sodium and thereafte with water until the wash waters were neutral and finally The extrac wa then evaporated under to and the solid residue obtained was crystallized from isopropyl After vacuum filtering and drying gm of 5 79 were This product occurred in the form of colorless having melting point of and a specif rotation in The product was insoluble in and soluble in benzene and methylene This compound is not described in the literature 5 7 9 Step A solution of lithium acetylide in a tetrahydrofuran media was by allowing acetylene to bubble through a mixture of cc of and 1560 cc of solution in over a period of 3 hours at This solution was heated to over a period of 5 gm 5 79 dissolved in 175 cc of were The was heated to reflux for 2 then cooled to and within a period of 30 without exceeding 3000 cc of an aqueous saturated solu ion of ammonium chloride were introduced The solution was The aqueous phase was separated and extracted with The combined organic phases with dried over sodium sulfate and evaporated to A resin thus which was dissolved in methylene chloride and subjected to On elution chloride containing of gm of η Q were product was utilized as such the following This compound is not in the Step III Ac To a solution of of 5 7 in cc of acetic acid of sulfonic acid monohydrate were added at a temperature of For a period of 20 hours this mixture was agitated at a temperature of 600 cc of water were introduced in the reaction mixture and it was agitated 2 hours at The aqueous mixture was extracted with methylene The combined organic phases were washed successively with then with a saturated solution of sodium bicarbonate and finally with water until j the wash waters were dried over sodium sulfate and evaporated vacuum to In this manner a resin was which was dissolved in methylene and subjected to chromatography through silica On elution with methylene chloride containing of of 17 with Ac were The product obtained was as such for the following This compound is not described in he 1 ou of Pile 13036 5 7 with Ac were The product was utilized as such for the following compound is not described in the insufficientOCRQuality
Claims (1)
- out of 23183 13036 WHAT IS CLAIMED of the formula out File 13036 acid 2 to 7 carbon wherein Ac represents the acyl of an organic carboxylic acid havin from 2 to 7 carbon esterifying the resulting ho 5 7 by the action of an esterifying derivative of an organic carboxylic acid out of 23183 hydrating theethynyl function of the resulting ester of the formula wherein Ac represents the acyl an organic carboxylic acid having from 2 to 7 carbon by the action of water in the presence of a hydration of the formula 1 out of File 68 The process of Claim step wherein said oxidizing agent is chromic acid anhydride and the reaction is conducted in the presence of sulfuric acid in an acetonlc process of step wherein said ethynylating agent is lithium acetylide in a The process of step wherein said esterifying derivative of an organic carboxylic acid having from 2 to 7 carbon atoms is acetic acid anhydride in the presence of toluene sulfonic acid as a The process of Claim step wherein said hydration catalyst is a mercuric catalyst selected from the group consisting of mercury salt of sulfonamide and an ion exchange resin containing mercuric cations and the reaction i conducted in an Process for producing compounds as defined in Claim substantially as hereinbefore described and with reference to the as defined in Claim whenever obtained in a process a claimed any of Claims 8 to insufficientOCRQuality
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR968659A FR1492767A (en) | 1964-03-25 | 1964-03-25 | Bis nor-18, 19 13-alkylated progesterone and method of preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IL30956A true IL30956A (en) | 1969-02-27 |
Family
ID=8826345
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL2318365A IL23183A (en) | 1964-03-25 | 1965-03-19 | 13beta-n-propyl-18,19-bis-nor-progesterone and process of preparation thereof |
| IL3095565A IL30955A (en) | 1964-03-25 | 1965-03-19 | 13beta-n-propyl-des-a-and 4,5-seco-pregnene compounds and process for preparing same |
| IL3095665A IL30956A (en) | 1964-03-25 | 1965-03-19 | 13beta-n-propyl-des-a-gonatrien-5-ols and process for preparing same |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL2318365A IL23183A (en) | 1964-03-25 | 1965-03-19 | 13beta-n-propyl-18,19-bis-nor-progesterone and process of preparation thereof |
| IL3095565A IL30955A (en) | 1964-03-25 | 1965-03-19 | 13beta-n-propyl-des-a-and 4,5-seco-pregnene compounds and process for preparing same |
Country Status (12)
| Country | Link |
|---|---|
| AT (1) | AT267080B (en) |
| BE (1) | BE660827A (en) |
| BR (1) | BR6568071D0 (en) |
| CH (1) | CH435265A (en) |
| DE (1) | DE1468903A1 (en) |
| DK (1) | DK112871B (en) |
| ES (1) | ES310879A1 (en) |
| FR (1) | FR1492767A (en) |
| GB (4) | GB1084164A (en) |
| IL (3) | IL23183A (en) |
| NL (1) | NL6503835A (en) |
| SE (1) | SE314067B (en) |
-
0
- GB GB1084166D patent/GB1084166A/en active Active
- GB GB1084167D patent/GB1084167A/en active Active
- GB GB1084165D patent/GB1084165A/en active Active
- GB GB1084164D patent/GB1084164A/en active Active
-
1964
- 1964-03-25 FR FR968659A patent/FR1492767A/en not_active Expired
-
1965
- 1965-03-09 BE BE660827D patent/BE660827A/xx unknown
- 1965-03-17 DK DK135065A patent/DK112871B/en unknown
- 1965-03-19 IL IL2318365A patent/IL23183A/en unknown
- 1965-03-19 IL IL3095565A patent/IL30955A/en unknown
- 1965-03-19 IL IL3095665A patent/IL30956A/en unknown
- 1965-03-23 DE DE19651468903 patent/DE1468903A1/en not_active Withdrawn
- 1965-03-23 ES ES0310879A patent/ES310879A1/en not_active Expired
- 1965-03-23 CH CH402365A patent/CH435265A/en unknown
- 1965-03-23 SE SE376765A patent/SE314067B/xx unknown
- 1965-03-24 BR BR16807165A patent/BR6568071D0/en unknown
- 1965-03-25 AT AT276165A patent/AT267080B/en active
- 1965-03-25 NL NL6503835A patent/NL6503835A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SE314067B (en) | 1969-09-01 |
| GB1084165A (en) | |
| GB1084164A (en) | |
| GB1084167A (en) | |
| IL23183A (en) | 1969-01-29 |
| BE660827A (en) | 1965-09-09 |
| DE1468903A1 (en) | 1969-01-16 |
| FR1492767A (en) | 1967-08-25 |
| ES310879A1 (en) | 1965-06-01 |
| NL6503835A (en) | 1965-09-27 |
| CH435265A (en) | 1967-05-15 |
| DK112871B (en) | 1969-01-27 |
| GB1084166A (en) | |
| IL30955A (en) | 1969-02-27 |
| AT267080B (en) | 1968-12-10 |
| BR6568071D0 (en) | 1973-08-07 |
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