SU383287A1 - METHOD FOR OBTAINING 7a-METHYL-17A-ETHYNYLESTRADIOL-3-CYCLOPENTYL ETHER It is well known that the condensation of acetylene with ca. bilonium compounds can be carried out using alkali metal derivatives. The application of the known reaction allowed us to obtain a new compound, possessing valuable properties. = 0 expose the exchange reaction with an acetylene-metallic compound, mainly with the acetylene compound according to Grignard or with an alkali metal acetylenide, with the isolation of the target product by known methods. Thus, a ketone of the above formula can be treated with acetylene in the presence of an alkali metal alkali metal, for example, ethyl, sodium or tertiary sodium amylate .10 This reaction is carried out in the usual way, if desired, in the presence of a catalyst in an organic solvent, for example, boiling alkanol ( ethanol, butanol, dimethyl glycol ether) or carbohydrate-15 of the genus (benzene, toluene, cyclohexane or cyclopentane), or dimethyl sulfoxide, or liquid ammonia. - Google Patents
METHOD FOR OBTAINING 7a-METHYL-17A-ETHYNYLESTRADIOL-3-CYCLOPENTYL ETHER It is well known that the condensation of acetylene with ca. bilonium compounds can be carried out using alkali metal derivatives. The application of the known reaction allowed us to obtain a new compound, possessing valuable properties. = 0 expose the exchange reaction with an acetylene-metallic compound, mainly with the acetylene compound according to Grignard or with an alkali metal acetylenide, with the isolation of the target product by known methods. Thus, a ketone of the above formula can be treated with acetylene in the presence of an alkali metal alkali metal, for example, ethyl, sodium or tertiary sodium amylate .10 This reaction is carried out in the usual way, if desired, in the presence of a catalyst in an organic solvent, for example, boiling alkanol ( ethanol, butanol, dimethyl glycol ether) or carbohydrate-15 of the genus (benzene, toluene, cyclohexane or cyclopentane), or dimethyl sulfoxide, or liquid ammonia.Info
- Publication number
- SU383287A1 SU383287A1 SU6218A SU6218A SU383287A1 SU 383287 A1 SU383287 A1 SU 383287A1 SU 6218 A SU6218 A SU 6218A SU 6218 A SU6218 A SU 6218A SU 383287 A1 SU383287 A1 SU 383287A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- acetylene
- alkali metal
- reaction
- carried out
- compound
- Prior art date
Links
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title description 6
- 229910052783 alkali metal Inorganic materials 0.000 title description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 title description 4
- -1 acetylene compound Chemical class 0.000 title description 3
- 150000001340 alkali metals Chemical class 0.000 title description 3
- 229910052708 sodium Inorganic materials 0.000 title description 3
- 239000011734 sodium Substances 0.000 title description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title 1
- 238000009835 boiling Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 title 1
- 238000009833 condensation Methods 0.000 title 1
- 230000005494 condensation Effects 0.000 title 1
- CRRYCJOJLZQAFR-UHFFFAOYSA-N cyclohexane;pentane Chemical compound CCCCC.C1CCCCC1 CRRYCJOJLZQAFR-UHFFFAOYSA-N 0.000 title 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title 1
- BLRXYTIIKIPJQL-UHFFFAOYSA-N dicarbide(1-) Chemical compound [C-]#C BLRXYTIIKIPJQL-UHFFFAOYSA-N 0.000 title 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 title 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 title 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title 1
- 229910000765 intermetallic Inorganic materials 0.000 title 1
- 238000002955 isolation Methods 0.000 title 1
- 150000002576 ketones Chemical class 0.000 title 1
- 239000007788 liquid Substances 0.000 title 1
- 239000003960 organic solvent Substances 0.000 title 1
- 150000003385 sodium Chemical group 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HLCRYAZDZCJZFG-BDXSIMOUSA-N (8S,9S,13S,14S)-13-methyl-6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthrene Chemical compound C1CC2=CC=CC=C2[C@@H]2[C@@H]1[C@@H]1CCC[C@@]1(C)CC2 HLCRYAZDZCJZFG-BDXSIMOUSA-N 0.000 description 1
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 description 1
- LMKPHJYTFHAGHK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-(1-hydroxycyclopentyl)-2-phenylacetate Chemical compound C1CCCC1(O)C(C(=O)OCCN(CC)CC)C1=CC=CC=C1 LMKPHJYTFHAGHK-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- XDGBLAFHHLKULM-UHFFFAOYSA-N lithium;ethyne Chemical compound [Li+].[C-]#C XDGBLAFHHLKULM-UHFFFAOYSA-N 0.000 description 1
- WDDOQHLJFOUQMW-UHFFFAOYSA-N lithium;ethynyl(trimethyl)silane Chemical compound [Li+].C[Si](C)(C)C#[C-] WDDOQHLJFOUQMW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Description
вакууме, создаваемом водоструйным насосом. Выпадающий «сырой по степени чистоты продукт подвергают еще раз реакции обменного разложени с ацетиленидом лити при описанных услови х, реакционную смесь обрабатывают , как указано выще, и полученный продукт реакции в третий раз обрабатывают ацетиленидом лити . В результате последней обработки получают около 5,4 г маслообразного «сырого продукта, который раствор ют в смеси петролейного эфира с толуолом (1:1) и хроматографируют на 30-кратном по весу избыточном количестве силикагел . После элюировани толуолом и смесью толуола с этило-вым эфиро.м уксусной кислоты получают чис тый 3-циклопентилокси-7а-метил-17а-этинил17р-гидроксиА (°-эстратриен, который после многократной перекристаллизации из смеси метанола с водой и эфира с гексаном плавитс при 121 -122°С; + 2° (хлороформ). Исходный материал удаетс получить, например , следующим образом. 5,0 г 7а-метилэстрана добавл ют к раствору алкогол га натри , приготовленного в 40 мл этанола. Затем смесь кратковременно подогревают при мерно до 60°С; охлаждают, смешивают с 4,4 м,л циклопентилбромида и кип т т 18 час с обратным холодильником. Упаривают суспензию в вакууме, создаваемом водоструйным насосом, смешивают с 50 мл воды и экстрагируют трижды метиленхлоридом. Эксракт, промытый водой до нейтральной среды, высушивают упаривают в вакууме, создаваемом водоструйным насосом. Путем хроматографировани остатка на силикагеле получают чистый 3-циклопентилокси-7а-метил - 17а-оксо-Д (° эстратриен . Соединение, перекристаллизован-ное из смеси метиленхлорида с метанолом, плавитс при 136--137°С; а о+128°С (из хлороформа). Предмет изобретени 1. Способ получени 3-циклопентилового эфира 7а-метил-17а-этинилэстрадиола формулы отличающийс тем, что соединение формулы подвергают реакции обмена с ацетиленметаллическим соединением с выделением целевого продукта известными приемами. 2. Способ по п. 1, отличающийс тем, что в качестве ацетиленметаллического соединени примен ют соединение ацетилена по Гринь ру или ацетиленид щелочного металла.vacuum created by a water jet pump. The product, which is crude in the degree of purity, is subjected once again to exchange decomposition reactions with lithium acetylenide under the described conditions, the reaction mixture is treated as described above, and the resulting reaction product is treated for the third time with lithium acetylide. As a result of the last treatment, about 5.4 g of oily "crude product" is obtained, which is dissolved in a mixture of petroleum ether and toluene (1: 1) and chromatographed on an excess of silica gel 30 times by weight. After elution with toluene and a mixture of toluene and ethyl ester of acetic acid, pure 3-cyclopentyloxy-7a-methyl-17a-ethynyl-17p-hydroxyA is obtained (° -estratriene, which after repeated recrystallization from a mixture of methanol and water and ether with hexane, melts at 121 - 122 ° C; + 2 ° (chloroform). The starting material can be obtained, for example, as follows: 5.0 g of 7a-methylethran is added to a solution of sodium alcohol, prepared in 40 ml of ethanol. The mixture is then heated briefly at measured to 60 ° C; cooled, mixed with 4.4 m, l cyclopent evaporated in a vacuum created by a water jet pump, mixed with 50 ml of water and extracted three times with methylene chloride. The extract was washed with water to a neutral medium, dried and evaporated in a vacuum created by a water jet pump. on silica gel, pure 3-cyclopentyloxy-7a-methyl-17a-oxo-D is obtained (° estratriene. A compound recrystallized from a mixture of methylene chloride and methanol, melts at 136-137 ° C; and about + 128 ° C (from chloroform). The subject matter of the invention is 1. A method for producing a 7a-methyl-17a-ethinylestradiol 3-cyclopentyl ester of the formula ## STR00007 ## in which the compound of the formula is subjected to an exchange reaction with an acetylene-metal compound, and the desired product is isolated by known techniques. 2. A method according to claim 1, characterized in that a Grignu acetylene compound or an alkali metal acetylide is used as the acetylene-metal compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU6218A SU67151A1 (en) | 1944-08-26 | 1944-08-26 | Wireless telegraph training device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU6218A SU67151A1 (en) | 1944-08-26 | 1944-08-26 | Wireless telegraph training device |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| SU383287A1 true SU383287A1 (en) | |
| SU399116A1 SU399116A1 (en) | |
| SU4405A1 SU4405A1 (en) | 1928-01-31 |
| SU67151A1 SU67151A1 (en) | 1945-11-30 |
Family
ID=48246805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU6218A SU67151A1 (en) | 1944-08-26 | 1944-08-26 | Wireless telegraph training device |
Country Status (1)
| Country | Link |
|---|---|
| SU (1) | SU67151A1 (en) |
-
1944
- 1944-08-26 SU SU6218A patent/SU67151A1/en active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| SU902666A3 (en) | Method of preparing pleuromutiline glycoside derivatives | |
| EP0004621A2 (en) | Process for the multi-step preparation of zeaxanthine and alloxanthine starting from derivatives of cyclohexanon and cyclohexanol; derivatives of cyclohexanon and cyclohexanol | |
| Cromwell et al. | Epoxyketones. IV. 1 Stereostructure, Absorption Spectra and Three-ring Carbonyl Hyperconjugation | |
| SU383287A1 (en) | METHOD FOR OBTAINING 7a-METHYL-17A-ETHYNYLESTRADIOL-3-CYCLOPENTYL ETHER It is well known that the condensation of acetylene with ca. bilonium compounds can be carried out using alkali metal derivatives. The application of the known reaction allowed us to obtain a new compound, possessing valuable properties. = 0 expose the exchange reaction with an acetylene-metallic compound, mainly with the acetylene compound according to Grignard or with an alkali metal acetylenide, with the isolation of the target product by known methods. Thus, a ketone of the above formula can be treated with acetylene in the presence of an alkali metal alkali metal, for example, ethyl, sodium or tertiary sodium amylate .10 This reaction is carried out in the usual way, if desired, in the presence of a catalyst in an organic solvent, for example, boiling alkanol ( ethanol, butanol, dimethyl glycol ether) or carbohydrate-15 of the genus (benzene, toluene, cyclohexane or cyclopentane), or dimethyl sulfoxide, or liquid ammonia. | |
| SU676170A3 (en) | Method of obtaining 7-oxy-estradiols | |
| Warner et al. | Propellanes. 17. Bridgehead olefins via solvolysis of 10, 10-dibromo [4.3. 1] propellanes | |
| Heathcock et al. | Photochemistry of 1, 6-cyclodecadienes. II. Synthesis and photochemistry of 6-methyl-1, 6-cyclodecadien-3-one | |
| Carr et al. | Synthesis, Proton Magnetic Resonance, and Stereochemistry of Certain o-Tolylcyclohexanediols1 | |
| Berens et al. | The First Stereoselective Synthesis of Racemic. beta.-Multistriatin: A Pheromone Component of the European Elm Bark Beetle Scolytus multistriatus (Marsh.) | |
| Zhang et al. | Synthesis of α, β-Unsaturated Ketones via Enamines | |
| Herz et al. | Resin acids. XX. Structure of levopimaric acid dioxide | |
| Gravel et al. | Synthesis and photochemistry of 4, 4-diphenyl-γ-pyran. Di-π-methane rearrangement in a new chromophore | |
| US5191125A (en) | Procedure for the preparation of bicyclo [3.2.0]hept-2-en-7-ones | |
| US3331856A (en) | Method of preparing transhexahydroindanones | |
| US3344169A (en) | Novel 1-acyloxy-6-hydroxy-9-methyl-delta4(10)-octalins and -trans-decalins | |
| DE1793570A1 (en) | Process for the production of veratryl ketone | |
| Lambert et al. | Triple bond as a potential double donor in solvolytic participation | |
| US3849455A (en) | Process for preparing methyl and ethyl 3,11-dimethyl-7-ethyltrideca-2,6,10-trienoates | |
| France et al. | Total synthesis of modified steroids. II. 8. beta.-Methyl-D-homoestranes | |
| US4205000A (en) | Dibenzo-oxa-bicyclonona-2,6-dienes | |
| KR800000862B1 (en) | Process for preparing substitute indanyl-5-carboxylic acid | |
| Kierstead et al. | 16-Oxa Steroids | |
| SU780435A1 (en) | 3,4-dihydro-10oxy-1(2h)-phenanthrenones as semi-product in synthesis of steroids or their analogues and method of obtaining same | |
| JP2880203B2 (en) | Preparation of furanone derivatives | |
| Padwa et al. | Grubbs and Wilkinson catalyzed reactions of 2-phenyl-3-vinyl substituted 2H-azirines |