CH155117A - Process for the preparation of an intermediate product for dyes of the benzanthrone series. - Google Patents
Process for the preparation of an intermediate product for dyes of the benzanthrone series.Info
- Publication number
- CH155117A CH155117A CH155117DA CH155117A CH 155117 A CH155117 A CH 155117A CH 155117D A CH155117D A CH 155117DA CH 155117 A CH155117 A CH 155117A
- Authority
- CH
- Switzerland
- Prior art keywords
- selenium
- solvent
- product
- dyes
- bromobenzanthrone
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- HUKPVYBUJRAUAG-UHFFFAOYSA-N 7-benzo[a]phenalenone Chemical class C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=CC2=C1 HUKPVYBUJRAUAG-UHFFFAOYSA-N 0.000 title claims description 6
- 239000013067 intermediate product Substances 0.000 title claims description 5
- 239000000975 dye Substances 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 229910052711 selenium Inorganic materials 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- RPGSDUFFVUBVQB-UHFFFAOYSA-N 1-bromobenzo[b]phenalen-7-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C3=C2C1=CC=C3Br RPGSDUFFVUBVQB-UHFFFAOYSA-N 0.000 claims 2
- 230000001419 dependent effect Effects 0.000 claims 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims 1
- 229940117389 dichlorobenzene Drugs 0.000 claims 1
- 238000009835 boiling Methods 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- GHCLXCSFSGRWIE-UHFFFAOYSA-N 1-(7-oxobenzo[a]phenalen-1-yl)sulfanylbenzo[b]phenalen-7-one Chemical class C1=CC2=CC=CC(C(=O)C=3C4=CC=CC=3)=C2C4=C1SC1=CC=C2C3=C1C1=CC=CC=C1C(=O)C3=CC=C2 GHCLXCSFSGRWIE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QVXFGVVYTKZLJN-KHPPLWFESA-N [(z)-hexadec-7-enyl] acetate Chemical compound CCCCCCCC\C=C/CCCCCCOC(C)=O QVXFGVVYTKZLJN-KHPPLWFESA-N 0.000 description 1
- IQTMWNQRJYAGDL-UHFFFAOYSA-N [SeH2]=[Se] Chemical class [SeH2]=[Se] IQTMWNQRJYAGDL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BSIHWSXXPBAGTC-UHFFFAOYSA-N isoviolanthrone Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C(C4=C56)=CC=C5C5=CC=CC=C5C(=O)C6=CC=C4C4=C3C2=C1C=C4 BSIHWSXXPBAGTC-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 sulfur halides Chemical class 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung eines Zwischenproduktes für Farbstoffe- der Benzanthronreihe. In der deutschen Patentschrift Nr. 264941 ist ein Verfahren zur Herstellung von Di- seleniden der Anthrachinonreihe, in der deut schen Patentschrift Nr.441748 ein solches zur Behandlung von Benzanthron mit Schwe- felhalogeniden und in der deutschen Patent- schrift Nr.
462154 ein Verfahren zur Her stellung von Benzanthronylsulfiden beschrie ben.
Gemäss vorliegender Erfindung wird eine Verbindung von wahrscheinlich folgender Formel erhalten
EMI0001.0016
Diese Verbindung (Dibenzanthronylselenid) kann hergestellt werden durch Erhitzen von Bz-1-Brombenzanthron mit Selenpulver in einem hochsiedenden Lösungsmittel mit oder ohne Zusatz eines leicht mit Brom, Brom- wasserstoffsäure oder beiden reagierenden Stoffes. Die neue Verbindung kristallisiert aus geeigneten Lösungsmitteln in dicken, spitzen Nadeln von goldgelber Farbe.
Die Reaktion verläuft hierbei vermutlich wie folgt:
EMI0001.0023
<I>Beispiel 1:</I> 100 Gewichtsteile Bz-1-Brombenzanthron, 14 Gewichtsteile feingepulvertes Selen und 20 Gewichtsteile gepulverter Kalk werden unter starkem Rühren in 500 Gewichtsteilen hochsiedendem Petroleum 8 Stunden auf 220 0 C erhitzt oder bis das feste Reaktions produkt, wenn in konzentrierter Schwefel säure gelöst, eine kräftige grünblaue Färbung ergibt. Da Bz-1-Brombenzanthron sich in Schwefelsäure mit roter Farbe löst, so gibt diese Farbenprobe einen guten Hinweis für die Beurteilung des Verlaufes der Reaktion.
Nach beendeter Reaktion wird die Mischung auf 50 0 C abgekühlt, filtriert, der Filter rückstand gründlich mit heissem Wasser ge waschen, getrocknet und schliesslich mit Salz säure vom Kalk befreit.
<I>Beispiel 2:</I> Eitle Lösung von 100 Gewichtsteilen Bz 1-Brombenzarithron in 300 Gewichtsteilen Trichlorbenzol wird mit 200 Gewichtsteilen hochsiedendem Petroleum und 14 Gewichts teilen Selen versetzt und das Ganze darin auf 210-220 0 C erhitzt, bis das Reaktions produkt in konzentrierter Schwefelsäure eine grünblaue Lösung ergibt. Die Lösung wird alsdann abgekühlt, das Reaktionsprodukt ab filtriert und getrocknet. Das so erhaltene Produkt gleicht dem nach Beispiel 1 er haltenen, ist aber frei von Kalk oder an organischen Salzen.
Es stellt ein körniges, gelbbraunes Pulver dar, das wenig löslich in kalten organischen Lösungsmitteln, aber ziemlich gut löslich in heissem Nitrobenzol oder Orthodichlorbenzol ist, aus denen es in dicken, spitzen Nadeln von goldgelber Farbe auskristallisiert. In konzentrierter Schwefelsäure löst es sich mit kräftiger, reiner grünblauer .Farbe. Es ist praktisch unlöslich in alkalischem Natrium hyposulfit.
Nach erfolgtem Auslaugen mit einer Schwefelnatriumlösung zur Entfernung überschüssigen Selens und Umkristallisieren in Nitrobenzol zeigt das Produkt einen Schmelzpunkt von<B>336-3370</B> C und einen Selengehalt von 14,97 %. Der theoretische Selengehalt des Bz-1-Bz-li-Dibenzarithronyl- selenides beträgt 14,740o.
Art Stelle von Kalk können auch andere Stoffe, die mit Brom oder Bromwasserstoff säure zu reagieren vermögen, Verwendung finden, so zum Beispiel Natriumacetat, Na triumsulfit, Natriumbisulfit, Natriumkarbonat oder Natriumbenzoat. An Stelle der genann ter. Natriumsalze können auch die entspre chenden Ammonium- oder Kaliumsalze ver wendet werden. Des weiteren kann matt auch Ammoniakgas über die kochende Mischung leiten, um ein gleiches Resultat zu erzielen.
Zwar können alle hochsiedenden. Lösungs mittel (ebenso auch niedrigsiedende unter entsprechendere Druck) bei diesem Verfahren benutzt werden, indessen empfiehlt es sich doch mehr, ein leicht halogenierbares oder ein Lösungsmittel mit hohem Wasserstoff- gehalt zu verwenden, wie zum Beispiel hoch siedende Petroleumöle, hydrierte Naphtaline, wie Di-, Tetra-, Hexa- oder Dekahydronaph- talin, Kerosen,
Paraffinöl oder Trichlorbenzol in Mischung mit einem oder mehreren der sogenannten Lösungsmittel.
Die neue Selenverbindung der - Benzan- throni-eihe ist ein wertvolles Zwischenprodrikt für die Herstellung von Benzanthronküpen- farbstoffen. Durch Behandeln dieses Zwischen produktes entweder für sich allein oder in Verbindung mit Benzanthron mit Hilfe alka lischer .Kondensationsmittel erhält man Iso- violanthron von hoher Reinheit.
Process for the production of an intermediate product for dyes of the benzanthrone series. German patent specification No. 264941 describes a process for the preparation of di-selenides of the anthraquinone series, German patent specification No. 441748 describes a process for treating benzanthrone with sulfur halides and German patent specification No.
462154 a process for the manufacture of benzanthronyl sulfides described ben.
According to the present invention, a compound of probably the following formula is obtained
EMI0001.0016
This compound (dibenzanthronyl selenide) can be prepared by heating Bz-1-bromobenzanthrone with selenium powder in a high-boiling solvent with or without the addition of a substance which reacts easily with bromine, hydrobromic acid or both. The new compound crystallizes from suitable solvents in thick, pointed needles of golden yellow color.
The reaction here is probably as follows:
EMI0001.0023
<I> Example 1: </I> 100 parts by weight of Bz-1-bromobenzanthrone, 14 parts by weight of finely powdered selenium and 20 parts by weight of powdered lime are heated with vigorous stirring in 500 parts by weight of high-boiling petroleum for 8 hours at 220 ° C. or until the solid reaction product when dissolved in concentrated sulfuric acid, it has a strong green-blue color. Since Bz-1-bromobenzanthrone dissolves in sulfuric acid with a red color, this color sample gives a good indication for assessing the course of the reaction.
After the reaction has ended, the mixture is cooled to 50 ° C., filtered, the filter residue is washed thoroughly with hot water, dried and finally freed from lime with hydrochloric acid.
<I> Example 2: </I> Eitle solution of 100 parts by weight of Bz 1-bromobenzarithrone in 300 parts by weight of trichlorobenzene is mixed with 200 parts by weight of high-boiling petroleum and 14 parts by weight of selenium and the whole is heated to 210-220 ° C. until the reaction occurs product in concentrated sulfuric acid results in a green-blue solution. The solution is then cooled, the reaction product is filtered off and dried. The product obtained in this way is similar to that obtained in Example 1, but is free of lime or organic salts.
It is a granular, yellow-brown powder that is sparingly soluble in cold organic solvents, but fairly soluble in hot nitrobenzene or orthodichlorobenzene, from which it crystallizes in thick, pointed needles of golden yellow color. In concentrated sulfuric acid, it dissolves with a strong, pure green-blue color. It is practically insoluble in alkaline sodium hyposulfite.
After leaching with a sodium sulfur solution to remove excess selenium and recrystallization in nitrobenzene, the product has a melting point of 336-3370 C and a selenium content of 14.97%. The theoretical selenium content of the Bz-1-Bz-li-dibenzarithronyl selenide is 14.740o.
Other substances that are able to react with bromine or hydrobromic acid can also be used, for example sodium acetate, sodium sulfite, sodium bisulfite, sodium carbonate or sodium benzoate. Instead of the one mentioned. Sodium salts, the corresponding ammonium or potassium salts can also be used. Furthermore, matt can also pass ammonia gas over the boiling mixture to achieve the same result.
All can boilers. Solvents (as well as low-boiling ones under more pressure) can be used in this process, but it is more advisable to use a solvent that is easily halogenated or a solvent with a high hydrogen content, such as high-boiling petroleum oils, hydrogenated naphthalene, such as , Tetra-, hexa- or decahydronaphthalene, kerosene,
Paraffin oil or trichlorobenzene mixed with one or more of the so-called solvents.
The new selenium compound of the Benzanthroni series is a valuable intermediate product for the manufacture of benzanthrone vat dyes. By treating this intermediate product either on its own or in conjunction with benzanthrone with the help of alkaline condensation agents, isoviolanthrone of high purity is obtained.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US155117XA | 1930-02-11 | 1930-02-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH155117A true CH155117A (en) | 1932-06-15 |
Family
ID=21771827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH155117D CH155117A (en) | 1930-02-11 | 1931-02-06 | Process for the preparation of an intermediate product for dyes of the benzanthrone series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH155117A (en) |
-
1931
- 1931-02-06 CH CH155117D patent/CH155117A/en unknown
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