DE512820C - Process for the preparation of oxyanthraquinone derivatives, in particular alizarin and its derivatives - Google Patents
Process for the preparation of oxyanthraquinone derivatives, in particular alizarin and its derivativesInfo
- Publication number
- DE512820C DE512820C DES83344D DES0083344D DE512820C DE 512820 C DE512820 C DE 512820C DE S83344 D DES83344 D DE S83344D DE S0083344 D DES0083344 D DE S0083344D DE 512820 C DE512820 C DE 512820C
- Authority
- DE
- Germany
- Prior art keywords
- derivatives
- alizarin
- oxyanthraquinone
- anthraquinone
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- 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 title description 13
- 239000003513 alkali Substances 0.000 claims description 4
- 150000004056 anthraquinones Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- RZVHIXYEVGDQDX-UHFFFAOYSA-N Anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- ASDLSKCKYGVMAI-UHFFFAOYSA-N 9,10-dioxoanthracene-2-carboxylic acid Chemical class C1=CC=C2C(=O)C3=CC(C(=O)O)=CC=C3C(=O)C2=C1 ASDLSKCKYGVMAI-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 11
- 239000000155 melt Substances 0.000 description 6
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YZHUMGUJCQRKBT-UHFFFAOYSA-M Sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229940080281 sodium chlorate Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000004345 1,2-dihydroxyanthraquinones Chemical class 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- -1 halogen derivatives of anthraquinone Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
Description
Verfahren zur Herstellung von Oxyanthrachinonderivaten, insbesondere Alizarin und seinen Derivaten Die Erfindung betrifft ein Verfahren zur Herstellung von Oxyanthrachinonderivaten, insbesondere Alizarin und seinen Derivaten.Process for the preparation of oxyanthraquinone derivatives, in particular Alizarin and its derivatives The invention relates to a process for the preparation of oxyanthraquinone derivatives, in particular alizarin and its derivatives.
Es ist bekannt, Oxyanthrachinonderivate, z. B. Alizarin, durch die Einwirkung von Alkalien sowohl auf Sulfonsäuren, z. B. Anthrachinon-ß-sulfonsäure, und Halogenderivate des Anthrachinons, z. B. PP-Chloranthrachinon, als auch auf 2-Oxyanthrachinon und 2-Aminoanthrachinon herzustellen.It is known to use oxyanthraquinone derivatives, e.g. B. Alizarin, by the Action of alkalis on both sulfonic acids, e.g. B. Anthraquinone-ß-sulfonic acid, and halogen derivatives of anthraquinone, e.g. B. PP-chloranthraquinone, as well To produce 2-oxyanthraquinone and 2-aminoanthraquinone.
Ferner ist bekannt, daß Anthrachinon-2-carbonsäure bei der Alkalischmelze in ein Oxyanthrachinonderivat, die x-Ox"-2-anthrachinoncarbonsäure, übergeführt wird.It is also known that anthraquinone-2-carboxylic acid in the alkali melt converted into an oxyanthraquinone derivative, the x-Ox "-2-anthraquinone carboxylic acid will.
Man hat auch schon 2-Alkylanthrachinone mit alkoholischer Kalilauge, gegebenenfalls unter Zusatz von Oxydationsmitteln, erhitzt, ohne daß dabei die Bildung von Alizarin beobachtet wurde; vielmehr gelangte man zu einem Kondensationsprodukt des P-substituierten Anthrachinons.You also have 2-alkylanthraquinones with alcoholic potassium hydroxide solution, optionally with the addition of oxidizing agents, heated without the formation has been observed by alizarin; rather, a condensation product was obtained of the P-substituted anthraquinone.
Überraschend wurde nun gefunden, daß man beim Erhitzen von Anthrachinonderivaten, die P-ständige kohlenstoffhaltige Gruppen enthalten, deren Kohlenstoffatom direkt an den Anthrachinonring gebunden ist, in einer wässerigen Lösung von Atzalkali, gegebenenfalls in Gegenwart eines Oxydationsmittels, Oxyanthrachinone, besonders Alizarin, erhält. Zweckmäßig wird dabei die Reaktion in einem Autoklaven bei 18o' durchgeführt. Gegenüber dem bekannten Verfahren der Herstellung von Alizarin hat dieses also den großen Vorteil, daß es in wässeriger Lösung ausgeführt wird, wobei sich Überhitzungen leichter vermeiden lassen als bei Schmelzreaktionen.It has now surprisingly been found that when anthraquinone derivatives are heated, the P-position carbon-containing groups, whose carbon atom directly bound to the anthraquinone ring in an aqueous solution of caustic alkali, optionally in the presence of an oxidizing agent, especially oxyanthraquinones Alizarin, receives. The reaction is expediently carried out in an autoclave at 18o ' carried out. Has compared to the well-known process of producing alizarin So this has the great advantage that it is carried out in aqueous solution, whereby overheating can be avoided more easily than with melting reactions.
Durch die Erfindung ist es möglich geworden, Alizarin und andere Oxyantrachinone aus sehr billig erhältlichen Zwischenprodukten, besonders aus 2-Methylanthrachinon, herzustellen, das seinerseits leicht in ausgezeichneter Reinheit aus Toluol und Phthalsäureanhydrid nach einer Abart der Friedel-Crafts-Synthese gewonnen werden kann.With the invention it has become possible to use alizarin and other oxyantraquinones from very cheap intermediate products, especially from 2-methylanthraquinone, produce, which in turn easily in excellent purity from toluene and Phthalic anhydride can be obtained according to a variant of the Friedel-Crafts synthesis can.
Nachstehend ist die Erfindung an einigen Ausführungsbeispielen erläutert. Teile bedeuten Gewichtsteile. Beispiel r zg Teile Anthrachinon-t3-carbonsäure werden in z 25o Teilen Ätznatronlösung, die 25o Teile Ätznatron und 6 Teile Natriumchlorat enthält, aufgelöst. Die Mischung wird dann in einen Autoklaven gebracht und unter gutem Rühren 24 Stunden lang auf 18o' erhitzt. Hierauf kann die Schmelze in bekannter Weise aufgearbeitet werden, beispielsweise durch Eingießen in Wasser und Ansäuern, oder aber man läßt die Schmelze abkühlen und filtriert dann das Alkalisalz des Alizarins, das dann auskristallisiert ist, durch ein geeignetes Filter, beispielsweise Monelmetalltuch. In diesem Falle enthalten die Filtrate das überschüssige Alkali. Sie können dann für weitere Schmelzen verwendet werden. Der Alizarinpreßkuchen wird dann auf dem gewöhnlichen Wege auf Allzarin verarbeitet. Beispiel 2 6o Teile ß-Methylanthrachinon, 252 Teile Ätznatron, =q. Teile Natriumchlorat und ggo Teile Wasser werden miteinander gemischt und in einem Autoklaven unter Rühren 24 Stunden lang bei =8o ° C erhitzt. Man läßt dann die Schmelze abkühlen, das abgeschiedene Natriumsalz des Alizarins wird aus der Mutterlauge abfiltriert. Das Alizarinsalz wird in siedendem Wasser gelöst, worauf von unverändertem 2-Methylanthrachinon abfiltriert wird. Aus dem Filtrat wird das freie Allzarin durch Ansäuern ausgefällt.The invention is explained below using a few exemplary embodiments. Parts mean parts by weight. Example r zg parts of anthraquinone-t3-carboxylic acid in z 25o parts caustic soda solution, the 25o parts caustic soda and 6 parts sodium chlorate contains, dissolved. The mixture is then placed in an autoclave and under good stirring for 24 hours heated to 18o '. The melt can then be used in a known Be worked up in a way, for example by pouring into water and acidifying, or you leave them Cool the melt and then filter the Alkali salt of alizarin, which is then crystallized, through a suitable filter, for example Monel metal cloth. In this case the filtrates contain the excess Alkali. They can then be used for further melts. The alizarin press cake is then processed in the usual way on Allzarin. Example 2 6o parts ß-methylanthraquinone, 252 parts caustic soda, = q. Parts of sodium chlorate and ggo parts Water are mixed together and placed in an autoclave with stirring for 24 hours heated for a long time at = 80 ° C. The melt is then allowed to cool, the deposited The sodium salt of alizarin is filtered off from the mother liquor. The alizarin salt is dissolved in boiling water, whereupon unchanged 2-methylanthraquinone is filtered off will. The free allzarin is precipitated from the filtrate by acidification.
Die nach der Entfernung des Alkalisalzes des Alizarins aus der abgekühlten Schmelze zurückbleibenden Ätznatronlaugen können bei den folgenden Schmelzen wieder Verwendung finden.The after the removal of the alkali salt of the alizarin from the cooled Caustic soda lye that remains in the melt can reappear in the subsequent melts Find use.
Die in den Beispielen angegebenen Mengenverhältnisse von Anthrachinonderivaten, Oxydationsmitteln, Ätzalkalien und Wasser können beträchtlich geändert werden.The proportions of anthraquinone derivatives given in the examples, Oxidizers, caustic alkalis, and water can be changed considerably.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB512820X | 1926-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE512820C true DE512820C (en) | 1930-11-17 |
Family
ID=10459395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DES83344D Expired DE512820C (en) | 1926-12-29 | 1927-12-29 | Process for the preparation of oxyanthraquinone derivatives, in particular alizarin and its derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE512820C (en) |
-
1927
- 1927-12-29 DE DES83344D patent/DE512820C/en not_active Expired
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