SU444768A1 - The method of obtaining 4 / (benzimidazolyl-2) -methylene / -lyoxolane derivatives1,3 - Google Patents
The method of obtaining 4 / (benzimidazolyl-2) -methylene / -lyoxolane derivatives1,3Info
- Publication number
- SU444768A1 SU444768A1 SU1854236A SU1854236A SU444768A1 SU 444768 A1 SU444768 A1 SU 444768A1 SU 1854236 A SU1854236 A SU 1854236A SU 1854236 A SU1854236 A SU 1854236A SU 444768 A1 SU444768 A1 SU 444768A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- benzimidazolyl
- methylene
- methyl
- dioxolane
- obtaining
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CPNOLRCHNQZMKO-UHFFFAOYSA-N 2-ethynyl-1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C(C#C)=NC2=C1 CPNOLRCHNQZMKO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- HCADUAJGZJLOLX-UHFFFAOYSA-N 2-ethynyl-1h-benzimidazole Chemical class C1=CC=C2NC(C#C)=NC2=C1 HCADUAJGZJLOLX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UMEHTUCYIDSLRJ-UHFFFAOYSA-N 4-methylidene-1,3-dioxolane Chemical class C=C1COCO1 UMEHTUCYIDSLRJ-UHFFFAOYSA-N 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- -1 aliphatic ketones Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Изобретение касаетс получени новых соединений - производных 4- (бензимидазолил-2 ) -метилен -диоксолана-1,3 формулы где RI, R2 и Ra - алкил; R4 - алкил или алкоксигрунпа. Эти соединени могут найти применение в качестве физиологически активных веществ и исходных продуктов дл органического синтеза . Способ получени 4-метилиден-1,3-диоксоланов путем конденсации производных ацетилена с алифатическими кетонами неизвестен Предлагаемый способ заключаетс в том что 2-этинилбензимидазолы Формулы где Rs и R4 имеют указанные значени подвергают г заимоденствию с кетонами формулы где RI и R2 имеют указанные значени , в присутствии основного агента в среде растворител и выдел ют целевой продукт обычными приемами. Взаимодействие можно проводить в присутствии щелочи, например едкого кали, в среде органического растворител , нанример эфира , нри температуре от О до 20°С, или в присутствии щелочного металла, например натри , в жидком аммиаке. Пример 1. 2,2,5,5-Тетраметил-4-метилен - (1-метил-2-бензимидазолил) -1,3-диоксолан . К 0,67 г (12 ммоль) порошкового едкого кали в 5 мл сухого эфира при перемешивании и охлаждении лед ной водой прибавл ют 0,47 г (3 ммоль) 1-метил-2-этинилбензимидазола и 0,73 мл (10 ммоль) ацетона в 2 мл эфира. Перемешивание продолжают 6 час при комнатной температуре (17-20°С). После разложени водой экстрагируют продукт реакции хлороформом и хроматографируют на окиси алюмини в смеси хлороформа и эфира, растворитель упаривают. Получают 0,5 г (61,5%)The invention relates to the preparation of new compounds - 4- (benzimidazolyl-2) -methylene-dioxolane-1,3 derivatives of the formula: where RI, R2 and Ra are alkyl; R4 is alkyl or alkoxygrupp. These compounds can be used as physiologically active substances and starting products for organic synthesis. The method of obtaining 4-methylidene-1,3-dioxolanes by condensation of acetylene derivatives with aliphatic ketones is unknown. The proposed method is that 2-ethynylbenzimidazoles Formulas where Rs and R4 have the indicated values, subject to the agreement with ketones of the formula where RI and R2 have the meanings in the presence of the main agent in the solvent medium and isolate the target product by conventional methods. The reaction can be carried out in the presence of an alkali, for example potassium hydroxide, in an organic solvent medium, an ether nanoparticle, at a temperature from 0 to 20 ° C, or in the presence of an alkali metal, for example sodium, in liquid ammonia. Example 1. 2,2,5,5-Tetramethyl-4-methylene - (1-methyl-2-benzimidazolyl) -1,3-dioxolane. 0.47 g (3 mmol) of 1-methyl-2-ethynylbenzimidazole and 0.73 ml (10 mmol) were added to 0.67 g (12 mmol) of powdered potassium hydroxide in 5 ml of dry ether with stirring and cooling with ice water. acetone in 2 ml of ether. Stirring is continued for 6 hours at room temperature (17-20 ° C). After decomposition with water, the reaction product is extracted with chloroform and chromatographed on alumina in a mixture of chloroform and ether, and the solvent is evaporated. Obtain 0.5 g (61.5%)
бесцветных нгл с т. пл. J73°C (из смеси диэтилового эфира с петролейным), легко растворимых в бензоле, ацетоне, спирте. Найдено, %: С 70,8; Н 7,4; N 10,1.colorless ngl with t. pl. J73 ° C (from a mixture of diethyl ether and petroleum), easily soluble in benzene, acetone, alcohol. Found,%: C 70.8; H 7.4; N 10.1.
Ci6H2oN202Ci6H2oN202
Вычислено, %: С 70,5; Н 7,4; N 10,3. Пример 2. 2,5-Диметил-2,5-диэтил-4-метилен- (Г-метил-2-бензимидазолил) -1,3-диоксолан .Calculated,%: C 70.5; H 7.4; N 10.3. Example 2. 2,5-Dimethyl-2,5-diethyl-4-methylene (G-methyl-2-benzimidazolyl) -1,3-dioxolane.
1-Метил-2-этинилбензимидазол ввод т в реакцию с метилэтилкетоном в услови х, описанных в примере 1. Продукт получают в виде светло-желтого масла. Выход 72-78%. Пикрат имеет т. пл. 178°С (из спирта).1-Methyl-2-ethynylbenzimidazole is reacted with methyl ethyl ketone under the conditions described in Example 1. The product is obtained as a light yellow oil. Yield 72-78%. Pikrat has t. Pl. 178 ° C (from alcohol).
Найдено, %: С 54,2; Н 5,3; N 13,2,Found,%: C 54.2; H 5.3; N 13.2,
Ci8H24N2O2 CsHsNsOCi8H24N2O2 CsHsNsO
Вычислено, %: С 54,4; Н 5,1; N 13,2.Calculated,%: C 54.4; H 5.1; N 13.2.
Пример 3. 2,5-Диметил-2,5-диэтил-4-метилен - (Г-метил-2-бензимидазолил) - 1,3-диоксолан .Example 3. 2,5-Dimethyl-2,5-diethyl-4-methylene - (G-methyl-2-benzimidazolyl) - 1,3-dioxolane.
0,28 г( 12 ммоль) металлического натри раствор ют Б 20 мл жидкого аммиака и добавл ют при перемешивании и охлаждении смесью углекислоты с ацетоном 0,94 г (6 моль) 1-метил-2-этинилбензимидазола и 1,1 мл (12 ммоль) метилэтилкетона в 10мл сухого эфира Перемешивают до испарени аммиака. После разложени водой экстрагируют продукт реакции хлороформом и хроматографируют на окиси алюмини в смеси хлороформа и эфира. Растворитель упаривают, получают 1,1 г (63%) 1,3-диоксолана в виде светло-желтого масла. Пикрат имеет т. нл. 178°С (из спирта).0.28 g (12 mmol) of metallic sodium is dissolved in B 20 ml of liquid ammonia and 0.94 g (6 mol) of 1-methyl-2-ethynylbenzimidazole and 1.1 ml (12 ml) are added with stirring and cooling with a mixture of carbon dioxide and acetone. mmol) of methyl ethyl ketone in 10 ml of dry ether. Stir until the ammonia evaporates. After decomposition with water, the reaction product is extracted with chloroform and chromatographed on alumina in a mixture of chloroform and ether. The solvent is evaporated, to obtain 1.1 g (63%) of 1,3-dioxolane in the form of a light yellow oil. Picrat has so nl. 178 ° C (from alcohol).
Найдено, %: С 54,2; Н 5,3; N 13,2.Found,%: C 54.2; H 5.3; N 13.2.
Ci8H24N2O2 CeHsNsOrCi8H24N2O2 CeHsNsOr
Вычислено, 7о: С 54,4; Н 5,1; N 13,2.Calculated 7o: C 54.4; H 5.1; N 13.2.
Пример 4. 2,2,5,5-Тетраметил-4-метилен - (Г-метил-5-метокси-2-бензимидазолил)-1 ,3-диоксолан.Example 4. 2,2,5,5-Tetramethyl-4-methylene - (G-methyl-5-methoxy-2-benzimidazolyl) -1, 3-dioxolane.
1-Метил-5-метокси- 2 -этинилбензнмидазол ввод т в реакцию с ацетоном в услови х, описанных в примере 1. Выход 1,3-диоксолана 75%. Продукт имеет вид желтоватых кристаллов с т. пл. 126°С (из петролейного эфира).1-Methyl-5-methoxy-2-ethynylbenznmidazole is reacted with acetone under the conditions described in Example 1. The yield of 1,3-dioxolane is 75%. The product has the appearance of yellowish crystals with m. Pl. 126 ° C (from petroleum ether).
Найдено, %: N9,3; Н 7,2; С 67,8. Вычислено, %: N 9,27; Н 7,1; С 68,1.Found,%: N9.3; H 7.2; C 67.8. Calculated,%: N 9.27; H 7.1; C 68.1.
Ci7H22N203Ci7H22N203
Пред м е т изобретени Prevention Invention
1. Способ получени производных 4- (бензимидазолил-2 )-метилен -диоксолана-1,3 формулы1. A method of producing 4- (benzimidazolyl-2) -methylene-dioxolane-1,3 derivatives of the formula
а)but)
где RI, R2 и Кз - алкил; R4 - алкил или алкоксигрунна, 90 отличающийс тем, что 2-этинилбензимидазолы формзлы с-снwhere RI, R2 and KS - alkyl; R4 is alkyl or alkoxygrune, 90 characterized in that 2-ethynylbenzimidazoles with cn-forms
(п(P
где Кз и R4 имеют указанные значени , нодвергают взаимодействию с кетонами формулыwhere Kz and R4 have the indicated meanings, they react with ketones of the formula
RR
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU1854236A SU444768A1 (en) | 1972-12-06 | 1972-12-06 | The method of obtaining 4 / (benzimidazolyl-2) -methylene / -lyoxolane derivatives1,3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU1854236A SU444768A1 (en) | 1972-12-06 | 1972-12-06 | The method of obtaining 4 / (benzimidazolyl-2) -methylene / -lyoxolane derivatives1,3 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU444768A1 true SU444768A1 (en) | 1974-09-30 |
Family
ID=20534249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU1854236A SU444768A1 (en) | 1972-12-06 | 1972-12-06 | The method of obtaining 4 / (benzimidazolyl-2) -methylene / -lyoxolane derivatives1,3 |
Country Status (1)
| Country | Link |
|---|---|
| SU (1) | SU444768A1 (en) |
-
1972
- 1972-12-06 SU SU1854236A patent/SU444768A1/en active
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