DE1262990B - Process for the production of anthraquinones - Google Patents
Process for the production of anthraquinonesInfo
- Publication number
- DE1262990B DE1262990B DEB88305A DEB0088305A DE1262990B DE 1262990 B DE1262990 B DE 1262990B DE B88305 A DEB88305 A DE B88305A DE B0088305 A DEB0088305 A DE B0088305A DE 1262990 B DE1262990 B DE 1262990B
- Authority
- DE
- Germany
- Prior art keywords
- groups
- anthrone
- anthraquinone
- nucleus
- oxidation
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/04—Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/24—Quinones containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
- C07C51/275—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids of hydrocarbyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. CL:Int. CL:
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
C 07 cC 07 c
Deutsche Kt.: 12 ο-10German kt .: 12 o-10
B88305 IVb/12 ο
3. August 1966
14. März 1968B88305 IVb / 12 ο
3rd August 1966
March 14, 1968
Es ist bekannt, daß man Anthron und dessen Derivate zu den entsprechenden Anthrachinonen oxydieren kann. Als Oxydationsmittel sind hierfür Braunstein in Schwefelsäure oder Chromsäure in Eisessig vorgeschlagen worden. Diese bekannten Verfahren sind jedoch unwirtschaftlich. So ist die Reinigung der durch Oxydation mit Braunstein in Schwefelsäure erhältlichen Produkte umständlich, und das Arbeiten in Chromsäure—Essigsäure erfordert größere Mengen an Essigsäure als Lösungsmittel, wodurch Chromsäure verlorengeht, die nur durch aufwendige Maßnahmen aus den anfallenden Lösungen regeneriert werden kann.It is known that anthrone and its derivatives are oxidized to the corresponding anthraquinones can. The oxidizing agents used are manganese dioxide in sulfuric acid or chromic acid in glacial acetic acid has been proposed. However, these known methods are uneconomical. Such is the purification the products obtainable by oxidation with manganese dioxide in sulfuric acid are cumbersome, and that Working in chromic acid — acetic acid requires larger ones Amounts of acetic acid as a solvent, whereby chromic acid is lost, which only by consuming Measures can be regenerated from the resulting solutions.
Aus der USA.-Patentschrift 3 163 657 ist ein Verfahren zur überführung von Anthron in Anthrachinon bekannt, bei dem man das Anthron in Pyridin als Lösungsmittel und in Gegenwart von Benzyltrimethylammoniumhydroxyd mit Luft oxydiert. Das Lösungsmittel wird anschließend durch Vakuumdestillation entfernt. Diese Arbeitsweise ist sehr umständlich und unwirtschaftlich. Sie liefert außerdem nur eine Ausbeute an Anthrachinon von 40%·US Pat. No. 3,163,657 discloses a process for converting anthrone into anthraquinone known, in which the anthrone in pyridine as a solvent and in the presence of benzyltrimethylammonium hydroxide oxidized with air. The solvent is then removed by vacuum distillation. This way of working is very cumbersome and uneconomical. In addition, it only provides an anthraquinone yield of 40%
Es wurde nun gefunden, daß man Anthrachinon, das in einer oder mehreren der Stellungen 1 bis 8 des Anthrachinonkerns durch Halogenatome, tertiäre Alkylgruppen, Arylgruppen, Aroylgruppen, Arylsulfonylgruppen, Carboxylgruppen oder solche Substituenten substituiert sein kann, die mit dem Anthrachinonkern anellierte chinoide Ringe bilden, durch Oxydation von Anthron, das in einer oder mehreren Stellungen 1 bis 8 des Anthronkerns durch Halogenatome, tertiäre Alkylgruppen, Arylgruppen, Aroylgruppen, Arylmercaptogruppen, Carboxylgruppen oder solche Substituenten substituiert sein kann, die mit dem Anthronkern aneHierte chinoide Ringe bilden, besonders vorteilhaft erhält, wenn man die Oxydation erfindungsgemäß mit einer wäßrigen, 5- bis 45gewichtsprozentigen Salpetersäure in mindestens stöchiometrischer Menge bei 150 bis 2500C durchführt. It has now been found that anthraquinone which can be substituted in one or more of the positions 1 to 8 of the anthraquinone nucleus by halogen atoms, tertiary alkyl groups, aryl groups, aroyl groups, arylsulfonyl groups, carboxyl groups or those substituents which form quinoid rings fused to the anthraquinone nucleus, by oxidation of anthrone, which can be substituted in one or more positions 1 to 8 of the anthrone nucleus by halogen atoms, tertiary alkyl groups, aryl groups, aroyl groups, aryl mercapto groups, carboxyl groups or those substituents which form aneHed quinoid rings with the anthrone nucleus are particularly advantageous if by carrying out the oxidation according to the invention with an aqueous, 5- to 45gewichtsprozentigen nitric acid in at least stoichiometric amount at 150 to 250 0 C.
Das als Ausgangsstoff zu verwendende Anthron, das bei der Umsetzung nach dem erfindungsgemäßen Verfahren unter Oxydation der Methylengruppe des Anthronkerns in Anthrachinon übergeht, kann in den Stellungen 1 bis 8 des Anthronkerns Halogenatome, wie Chlor- oder Bromatome, tertiäre Alkylgruppen, wie tertiäre Butylgruppen, Arylgruppen, wie Phenylgruppen, Aroylgruppen, wie Benzoylgruppen, Arylmercaptogruppen, wie Thiophenylgruppen oder Carboxylgruppen, sowie solche Substituenten enthalten, die mit dem Anthronkern anellierte chinoide Ringe bilden. Von den genannten möglichen Verfahren zur Herstellung von AnthrachinonenThe anthrone to be used as starting material, which in the implementation according to the invention Process converts into anthraquinone with oxidation of the methylene group of the anthrone nucleus, can in positions 1 to 8 of the anthrone nucleus halogen atoms, such as chlorine or bromine atoms, tertiary alkyl groups, such as tertiary butyl groups, aryl groups such as phenyl groups, aroyl groups such as benzoyl groups, Aryl mercapto groups such as thiophenyl groups or carboxyl groups, and such substituents which form quinoid rings fused with the anthrone core. Of the mentioned possible Process for the production of anthraquinones
Anmelder:Applicant:
Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden
Aktiengesellschaft, 6700 LudwigshafenAktiengesellschaft, 6700 Ludwigshafen
Als Erfinder benannt:Named as inventor:
Dr. Ernst Schefczik, 6700 LudwigshafenDr. Ernst Schefczik, 6700 Ludwigshafen, Germany
Substituenten gehen die Arylmercaptogruppen unter den Bedingungen der Umsetzung in Arylsulfonylgruppen über. Beispielsweise seien folgende Anthrone genannt: Anthron, 4-Chloranthron, 1,4-Dichloranthron, 1 -Phenylmercapto-4-chloranthron, 2,3-Dichloran thron, l,3-Dichloranthron-(9), 1,3-Dichloranthron-(lO), l,2,4-Trichloranthron-(9), 1,2,4-Trichloranthron-(lO), 1,2,3,4-Tetrachloranthron, 1,4-Dichlor-6-(oder 7)-tert.butylanthron-(9), l,4-Dichlor-6-broman thron -(10), 1,4 - Dichloranthron - (9) - carbonsäure-6-(oder7) oder die VerbindungenThe aryl mercapto groups are substituted under the conditions of the conversion into arylsulfonyl groups above. For example, the following anthrones may be mentioned: anthrone, 4-chloranthrone, 1,4-dichloranthrone, 1-phenylmercapto-4-chloranthrone, 2,3-dichlorane throne, 1,3-dichloranthrone- (9), 1,3-dichloranthrone- (10), 1,2,4-trichloranthrone- (9), 1,2,4-trichloranthrone- (10), 1,2,3,4-tetrachloranthrone, 1,4-dichloro-6- (or 7) -tert.butylanthron- (9), 1,4-dichloro-6-bromanthrone - (10), 1,4 - dichloranthrone - (9) - carboxylic acid 6- (or7) or the connections
ClCl
O ClO Cl
ClCl
Von diesen Anthronen werden bevorzugt solche eingesetzt, die durch direkte Synthese zugänglich sind und nicht nur durch Reduktion der entsprechenden Anthrachinone hergestellt werden, wie 1,4-Dichloranthron und 1,2,3,4-Tetrachloranthron.Of these anthrones, preference is given to using those which are accessible by direct synthesis and are not only produced by reducing the corresponding anthraquinones, such as 1,4-dichloroanthrone and 1,2,3,4-tetrachloroanthrone.
Als Oxydationsmittel wird eine wäßrige 15- bis 30gewichtsprozentige Salpetersäure bevorzugt. DasAn aqueous 15 to 30 percent strength by weight nitric acid is preferred as the oxidizing agent. That
809 518/690809 518/690
Oxydationsmittel wird, bezogen auf Salpetersäure, in mindestens stöchiometrischen Mengen angewendet. Vorteilhaft nimmt man jedoch einen Überschuß, beispielsweise eine 5- bis 20fache Gewichtsmenge Salpetersäure, bezogen auf Anthron.Oxidizing agent is used in at least stoichiometric amounts, based on nitric acid. However, it is advantageous to use an excess, for example 5 to 20 times the amount by weight of nitric acid, based on anthrone.
Im einzelnen führt man das neue Verfahren so aus, daß man das Gemisch aus Anthron und wäßriger Salpetersäure in einem Druckgefäß, wie Glasbombe, Rühr- oder Schüttelautoklav, auf eine Temperatur von 150 bis 250°C erhitzt und eine bis mehrere Stunden auf dieser Temperatur hält. Der Druck, der von der Füllung des Autoklavs abhängig ist, kann dabei bis zu 150 atü betragen.. Beim Erkalten scheidet sich das Anthrachinon aus der im Überschuß angewendeten wäßrigen Salpetersäure in reiner Form ab. Die Ausbeuten liegen bei dem neuen Verfahren bei Werten von 75 bis 98%.In detail, the new process is carried out in such a way that the mixture of anthrone and aqueous Nitric acid in a pressure vessel, such as a glass bomb, stirred or shaking autoclave, to a temperature heated from 150 to 250 ° C and held at this temperature for one to several hours. The pressure, which depends on the filling of the autoclave, can be up to 150 atmospheres. When cooling down the anthraquinone separates in pure form from the aqueous nitric acid used in excess away. The yields in the new process are between 75 and 98%.
Daß sich Anthrone in so glatter Reaktion mit Salpetersäure zu Anthrachinonen oxydieren lassen, ist-überraschend. In Liebigs Annalen der Chemie, 212 (1882), S. 7 und 8, wird zwar angegeben, daß Anthranol mit rauchender Salpetersäure zu Anthrachinon oxydiert wird, jedoch ist aus der deutschen Patentschrift 497 503 und Organic Syntheses, Coll. Vol. I, 2. Auflage, S. 390, bekannt, daß bei der Einwirkung von rauchender Salpetersäure auf Anthron Nitroverbindungen erhalten werden.That anthrones can be oxidized to anthraquinones in such a smooth reaction with nitric acid, is-surprising. In Liebigs Annalen der Chemie, 212 (1882), pp. 7 and 8, it is stated that Anthranol is oxidized to anthraquinone with fuming nitric acid, however it is from the German Patent 497,503 and Organic Syntheses, Coll. Vol. I, 2nd edition, p. 390, known that with the action from fuming nitric acid on anthrone nitro compounds.
Die nach dem erfindungsgemäßen Verfahren erhältlichen Anthrachinone sind wertvolle Zwischenprodukte, z. B. für die Herstellung von Farbstoffen.Those obtainable by the process according to the invention Anthraquinones are valuable intermediates, e.g. B. for the production of dyes.
Die in dem Beispiel genannten Teile und Prozente beziehen sich auf Gewichtseinheiten.The parts and percentages mentioned in the example relate to units by weight.
26,3 Teile 1,4-Dichloranthron und 120 Teile 18%ige wäßrige Salpetersäure werden in einem Schüttelautoklav aus rostfreiem Stahl innerhalb von 4 Stunden auf 200° C erhitzt und 2 Stunden bei dieser Temperatur gehalten. Nach dem Erkalten isoliert man 25,9 Teile 1,4-Dichloranthrachinon vom Schmelzpunkt 189 bis 1900C (aus Essigsäure).26.3 parts of 1,4-dichloroanthrone and 120 parts of 18% strength aqueous nitric acid are heated in a stainless steel shaking autoclave to 200 ° C. over the course of 4 hours and kept at this temperature for 2 hours. After cooling, 25.9 parts of 1,4-dichloroanthraquinone with a melting point of 189 to 190 ° C. (from acetic acid) are isolated.
Claims (2)
USA.-Patentschrift Nr. 3 163 657;
Liebigs Annalen der Chemie, 212 (1882), S. 7 und 8; E. C 1 a r, Aromatische Kohlenwasserstoffe, Berlin, 1941, S. 265.Considered publications:
U.S. Patent No. 3,163,657;
Liebigs Annalen der Chemie, 212 (1882), pp. 7 and 8; E. C 1 ar, Aromatic hydrocarbons, Berlin, 1941, p. 265.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19661568157 DE1568157A1 (en) | 1966-08-03 | 1966-08-03 | Process for the production of anthraquinone carboxylic acids |
DEB88305A DE1262990B (en) | 1966-08-03 | 1966-08-03 | Process for the production of anthraquinones |
FR115925A FR1533555A (en) | 1966-08-03 | 1967-07-27 | Process for the production of anthraquinones |
CH1079867A CH485635A (en) | 1966-08-03 | 1967-07-31 | Process for the production of anthraquinones |
CH1874169A CH485638A (en) | 1966-08-03 | 1967-07-31 | Process for the preparation of anthraquinone carboxylic acids |
GB3553867A GB1124439A (en) | 1966-08-03 | 1967-08-02 | Production of anthraquinones |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB0088306 | 1966-08-03 | ||
DEB88305A DE1262990B (en) | 1966-08-03 | 1966-08-03 | Process for the production of anthraquinones |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1262990B true DE1262990B (en) | 1968-03-14 |
Family
ID=25968038
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEB88305A Pending DE1262990B (en) | 1966-08-03 | 1966-08-03 | Process for the production of anthraquinones |
DE19661568157 Pending DE1568157A1 (en) | 1966-08-03 | 1966-08-03 | Process for the production of anthraquinone carboxylic acids |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19661568157 Pending DE1568157A1 (en) | 1966-08-03 | 1966-08-03 | Process for the production of anthraquinone carboxylic acids |
Country Status (3)
Country | Link |
---|---|
CH (1) | CH485635A (en) |
DE (2) | DE1262990B (en) |
GB (1) | GB1124439A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3163657A (en) * | 1962-06-13 | 1964-12-29 | United States Steel Corp | Process for the oxidation of partially hydrogenated polycyclic aromatic and heterocyclic compounds |
-
1966
- 1966-08-03 DE DEB88305A patent/DE1262990B/en active Pending
- 1966-08-03 DE DE19661568157 patent/DE1568157A1/en active Pending
-
1967
- 1967-07-31 CH CH1079867A patent/CH485635A/en not_active IP Right Cessation
- 1967-08-02 GB GB3553867A patent/GB1124439A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3163657A (en) * | 1962-06-13 | 1964-12-29 | United States Steel Corp | Process for the oxidation of partially hydrogenated polycyclic aromatic and heterocyclic compounds |
Also Published As
Publication number | Publication date |
---|---|
DE1568157A1 (en) | 1970-01-02 |
CH485635A (en) | 1970-02-15 |
GB1124439A (en) | 1968-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1793183B1 (en) | Process for the preparation of trimethyl-p-benzoquinone | |
DE1262990B (en) | Process for the production of anthraquinones | |
DE927333C (en) | Process for the reduction of nitroanthraquinones and separation of the reduction products | |
DE930751C (en) | Process for the preparation of terephthalic acid from p-xylylene dichloride | |
DE1643750C3 (en) | Process for the production of lactones with 6 to 13 ring members and isobutyric acid | |
DE3732015A1 (en) | 2-NEOPENTYLANTHRACHINONE, METHOD FOR PRODUCING 2-NEOPENTYLANTHRACHINONE AND THE USE THEREOF AS A CATALYST FOR H (ARROW DOWN) 2 (ARROW DOWN) O (ARROW DOWN) 2 (ARROW DOWN) MANUFACTURER | |
DE765011C (en) | Process for the preparation of aliphatic dicarboxylic acids | |
DE2029560C3 (en) | Process for the production of pure 3-methylbutane-13-diol | |
US2075455A (en) | Compounds of the dibenzanthrone series | |
DE1263737B (en) | Process for the production of anthraquinones | |
US2865933A (en) | Process for the preparation of anthraquinone | |
DE623752C (en) | ||
DE1233964B (en) | Process for the preparation of linear trans quinacridone quinones | |
DE2846432C2 (en) | ||
DE2300327A1 (en) | PROCESS FOR THE PRODUCTION OF 3-FLUOROSALICYLALDEHYDE | |
DE3641793A1 (en) | METHOD FOR PRODUCING ALKYL-SUBSTITUTED AROMATIC KETONES | |
DE1180760B (en) | Process for the preparation of optionally substituted 1, 5-diamino-4, 8-dihydroxy- or 1, 8-diamino-4, 5-dihydroxy-anthraquinones | |
DE1670214A1 (en) | Process for the preparation of tris (N-ss-hydroxyalkyl) isocyanuric acid | |
DE1183067B (en) | Process for the production of pyromellitic acid | |
DE1161881B (en) | Process for the preparation of 1, 2-epoxycyclododecadiene (5, 9) | |
AT256076B (en) | Process for the preparation of benzene carboxylic acids | |
DE1254269B (en) | Process for the preparation of linear trans quinocridone quinones | |
DE1915385A1 (en) | Process for the preparation of o-benzoylbenzoic acid | |
DE1793347A1 (en) | Process for the preparation of substituted cyanobutyric acids | |
CH485638A (en) | Process for the preparation of anthraquinone carboxylic acids |