SU53095A1 - The method of obtaining anthracene derivatives - Google Patents
The method of obtaining anthracene derivativesInfo
- Publication number
- SU53095A1 SU53095A1 SU53095A1 SU 53095 A1 SU53095 A1 SU 53095A1 SU 53095 A1 SU53095 A1 SU 53095A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- green
- anthracene derivatives
- anthraquinone
- red
- product
- Prior art date
Links
- 150000001454 anthracenes Chemical class 0.000 title description 4
- 238000000034 method Methods 0.000 title description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 7
- 150000004056 anthraquinones Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GCDBEYOJCZLKMC-UHFFFAOYSA-N 2-hydroxyanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 GCDBEYOJCZLKMC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
Из германского патента № 241806 известно, что при нагревании антрахинона со щелочами в присутствии сульфитов получаетс ализарин.From German Patent No. 241806, it is known that by heating anthraquinone with alkalis in the presence of sulphites, alizarin is obtained.
Авторами насто щего изобретени было найдено, что значительно более кратковременное взаимодействие реакционной смеси, подобной описанной в примере 3 названного патента, приводит к образованию вместе с продуктами восстановлени антрахинона, а иногда со следами ализарина, нового производного антрацена - продукта зеленого цвета, раствор ющегос в щелочи с желто-коричневым окрашиванием . Этот продукт имеет состав QHjoOg, кристаллизуетс из спирта и лед ной уксусной кислоты в зеленых иглах, плав щихс с почернением и спеканием при 274°. При дальнейшем нагревании он плавитс в пределах 303-ЗОб, выдел желтый возгон 2-оксиантрахинона.The authors of the present invention have found that a much shorter interaction of the reaction mixture, similar to the mentioned patent described in Example 3, leads to the formation of a new anthracene derivative, a product of green color, dissolved in alkali, with traces of the reduction of anthraquinone, and sometimes with traces of alizarin. with yellow brown staining. This product has the composition QHjoOg, crystallizes from alcohol and glacial acetic acid in green needles, melting with blackening and sintering at 274 °. Upon further heating, it melts within 303-30, separating the yellow sublimation of 2-hydroxyanthraquinone.
По анализу и свойствам продукт отвечает 2,9 - дигидро - 2,10 - диокси-9оксо-антрацену . Он может иметь значение дл синтеза промежуточных продуктов, красителей и фармацевтических препаратов.According to the analysis and properties of the product corresponds to 2,9 - dihydro - 2,10 - dioxy-9oxo-anthracene. It may be of importance for the synthesis of intermediates, dyes and pharmaceuticals.
Пример. 26 вес. ч, тонко измельченного антрахинона загружались в стальной автоклав с мешалкой, где предварительно находились 19, 5 вес. ч. едкого натра, 40,73 вес. ч. сульфита натри (38%) и 390 вес. ч. воды. После закрыти автоклава его нагревали до 210° в течение 1 часа и выдерживали при этой темлературе 5-6 часов. По охлаждении автоклава масса,-имевша темно-бурый цвет, выгружалась и фильтрованием отдел лс не вошедший в реакцию антрахинон. Фильтрат разбавл ли 390 ч. воды и продуванием воздуха через раствор достигали окислени нестойких продуктов восстановлени антрахинона в антрацен. Последний по осаждении собирали на фильтре и промывали. Щелочной маточник после подкислени сол ной кислотой выделил темно-зеленый осадок , который после промывки и переосаждени (привод щего к освобождению от следов ализарина, если они имеютс ) отвечает указанному выше составу.Example. 26 wt. h, finely ground anthraquinone was loaded into a steel autoclave with a stirrer, where 19, 5 wt. including caustic soda, 40,73 weight. including sodium sulfite (38%) and 390 wt. h of water. After closing the autoclave, it was heated to 210 ° for 1 hour and kept at this temperature for 5-6 hours. Upon cooling the autoclave, the mass, which was dark brown, was discharged and the unreacted anthraquinone was separated by filtration. The filtrate was diluted with 390 parts of water and the oxidation of the unstable products of the reduction of anthraquinone to anthracene was achieved by blowing air through the solution. The latter was collected on a filter and washed. The alkaline mother liquor, after acidification with hydrochloric acid, isolated a dark green precipitate, which, after washing and reprecipitation (leading to release from traces of alizarin, if any), corresponds to the composition indicated above.
Продукт раствор етс в этиловом и метиловом спирте с зеленым окрашиванием в эфире, с буровато-зеленым-в проход щем свете и с красным в отраженном. Лигроин, петролейный эфир, четыреххлористый углерод не раствор ют продукта. Он хорошо растворим в ацетоне с красным окрашиванием, в хлороформе с зеленым в проход шем и с красным в отраженном свете, в нитробензоле с зеленым , в пиридине с темным бурозеленым цветом. В ароматических углеводородах и в лед ной уксусной кислоте раствор етс , образу зеленый раствор в проход щем, красный в отраженном свете- Концентрированна серна кислота дает темно-бурокрасный раствор, выдел ющий при разбавлении водой вновь зеленый продукт. Щелочи раствор ют его с буро-желтым окрашиванием.The product is dissolved in ethyl and methyl alcohol with a green color on the air, brownish green in transmitted light and red in reflected. Lygroin, petroleum ether, carbon tetrachloride do not dissolve the product. It is highly soluble in acetone with red coloration, in chloroform with green in the passage, and with red in reflected light, in nitrobenzene with green, in pyridine with a dark brown-green color. In aromatic hydrocarbons and in glacial acetic acid, it dissolves, forming a green solution in the passing, red in reflected light. Concentrated sulfuric acid gives a dark red red solution, releasing again the green product upon dilution with water. Alkalis dissolve it with a brown-yellow staining.
Предмет изобретени .The subject matter of the invention.
Способ получени антраценовых производных путем нагревани антрахинона с водным раствором щелочи в присутствии сульфита, отличающийс тем, что, с целью получени 2,9 - дигидро-2,10-диокси-9-оксо-антрацена , реакцию провод т при 200 - 220° в течение 5-б часов, послечего обычными приемами отдел ют ализарин , антрахинон и продукты восстановлени последнего от.антраценового производного.The method of producing anthracene derivatives by heating anthraquinone with an aqueous solution of alkali in the presence of sulfite, characterized in that, in order to obtain 2.9 - dihydro-2,10-dioxy-9-oxo-anthracene, the reaction is carried out at 200 - 220 ° C. for 5b hours, alizarin, anthraquinone and the products of reduction of the latter from the anthracene derivative are separated by conventional methods.
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