DE153770C - - Google Patents
Info
- Publication number
- DE153770C DE153770C DENDAT153770D DE153770DA DE153770C DE 153770 C DE153770 C DE 153770C DE NDAT153770 D DENDAT153770 D DE NDAT153770D DE 153770D A DE153770D A DE 153770DA DE 153770 C DE153770 C DE 153770C
- Authority
- DE
- Germany
- Prior art keywords
- oxazine
- melt
- purpurin
- aniline
- gradually
- 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.)
- Active
Links
- BBNQQADTFFCFGB-UHFFFAOYSA-N 1,2,4-Trihydroxyanthraquinone Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims 1
- 238000006011 modification reaction Methods 0.000 claims 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2H-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003142 primary aromatic amines Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 B. azobenzene Chemical class 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N Mercury(II) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- QUDZIKKHBMBJKK-UHFFFAOYSA-N [N+](=O)([O-])OC1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O Chemical class [N+](=O)([O-])OC1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O QUDZIKKHBMBJKK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
- C09B5/30—1,2 azoles of the anthracene series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
<%i>uh«1l· tcA <% i> uh «1l · tcA
ϊιίΦ xi'iiüi-ii.i.
KAISERLICHES ϊιίΦ xi'iiüi-ii.i.
IMPERIAL
PATENTAMT.PATENT OFFICE.
In der Patentschrift 141575 ist gezeigt worden, daß man durch Oxydation von o-Arylidooxyanthrachinonen, welche eine Hydroxylgruppe benachbart zur Arylidogruppe enthalten, zu oxazinartigen Verbindungen der Anthracenreihe gelangt. Es wurde ferner gezeigt, daß man die Darstellung von a-Arylidooxyanthrachinonen und deren Überführung in Oxazine in der Weise zu einer Operation vereinigen kann, daß man in geeigneten Nitrooxyanthrachinonen zunächst die Nitrogruppe durch die Arylidogruppe ersetzt und die gebildeten a-Aryhdooxyanthrachinone im Augenblick des Entstehens in Oxazine überführt.In the patent specification 141575 is shown been that one by oxidation of o-Arylidooxyanthraquinones, which is a hydroxyl group Contained adjacent to the arylido group, leads to oxazine-like compounds of the anthracene series. It was further shown that one can prepare the preparation of a-Arylidooxyanthraquinones and their conversion in Oxazine can be combined into one operation in such a way that one in suitable Nitrooxyanthraquinones initially replaced the nitro group by the arylido group and the α-arythooxyanthraquinones formed Converted to Oxazine at the moment of creation.
Es wurde nun gefunden, daß man mittels einer Operation gleichfalls zu den beschriebenen Oxazinen gelangen kann, wenn man an Stelle des in dem genannten Verfahren verwendeten i-Nitro-2 · 4-dioxyanthrachinons das entsprechende Oxyanthrachinon (Purpurin) mit primären aromatischen Aminen oder deren Substitutionsprodukten kondensiert und hierbei die Bedingungen derart wählt, daß intermediär a-Arylidooxyanthrachinon (vergl. die Patentschrift 145239) gebildet wird.It has now been found that, by means of an operation, the described Oxazines can be obtained if you take the place of the procedure mentioned used i-nitro-2 4-dioxyanthraquinones the corresponding oxyanthraquinone (purpurin) condensed with primary aromatic amines or their substitution products and selects the conditions here in such a way that a-arylidooxyanthraquinone (cf. the patent 145239) is formed.
Das Verfahren besteht im allgemeinen darin, daß man Purpurin unter Zusatz geeigneter Kondensationsmittel, Oxydationsmittel und Sauerstoffüberträger mit primären aromatischen Aminen oder deren Substitutionsprodukten auf höhere Temperaturen, und zwar vorteilhaft auf 160 bis 2200 C, erhitzt. The process generally consists in heating purpurine to higher temperatures, advantageously to 160 to 220 ° C., with the addition of suitable condensing agents, oxidizing agents and oxygen carriers with primary aromatic amines or their substitution products.
Als Oxydationsmittel bezw. Sauerstoffüberträger können Sauerstoff, atmosphärische Luft, die Oxyde, Superoxyde und Salze der Schwermetalle, Nitrokörper, wie Nitrobenzol, Nitrotoluol oder ähnlich wirkende Stickstoffverbindungen, z. B. Azobenzol usw., verwendet werden.As an oxidizing agent respectively. Oxygen carriers can be oxygen, atmospheric Air, the oxides, super oxides and salts of heavy metals, nitro bodies such as nitrobenzene, Nitrotoluene or similar nitrogen compounds, e.g. B. azobenzene, etc. used will.
B e i s ρ i e 1 ι.B e i s ρ i e 1 ι.
In einem mit Rührwerk versehenen emaillierten Kessel werden 50 kg Purpurin und 5 kg Borsäure in 300 kg Anilin eingetragen und unter stetem Rühren auf 160 bis 2000 erhitzt. Man trägt sodann allmählich und in kleinen Anteilen 42 kg Quecksilberoxyd ein und hält die Schmelze so lange auf der angegebenen Temperatur, bis an herausgenommenen Proben eine Zunahme an Oxazin nicht mehr wahrnehmbar ist. Hierbei geht die anfangs gelbrote Farbe der Schmelze durch Violett in ein klares Blau über. Man arbeitet die vom Quecksilber abgegossene Schmelze in der üblichen Weise mit verdünnter Salzsäure auf, wäscht säurefrei und trocknet.In an agitator provided with enamelled boiler 50 kg purpurin and 5 kg of boric acid are introduced into 300 kg of aniline and heated under constant stirring to 160 to 200 0th Then gradually and in small portions 42 kg of mercury oxide are introduced and the melt is kept at the specified temperature until an increase in oxazine is no longer perceptible on the samples taken. The initially yellow-red color of the melt changes from violet to a clear blue. The melt cast off from the mercury is worked up in the usual way with dilute hydrochloric acid, washed acid-free and dried.
Durch Umkristallisieren des Rohproduktes aus Anilin, Pyridin usw. erhält man das Oxazin rein in Form bronzeglänzender, dunkler Nadeln, die sich mit blauer' Farbe in Anilin,This is obtained by recrystallizing the crude product from aniline, pyridine, etc. Oxazine purely in the form of shiny bronze, dark needles, which have a blue color in aniline,
Pyridin, grünblau in Schwefelsäure lösen. Der Körper ist identisch mit dem in Beispiel 5 der Patentschrift 141575 beschriebenen Oxazin aus i-Anilido-2 · 4-dioxyanthrachinon. Dissolve pyridine, green-blue in sulfuric acid. The body is identical to that in example 5 of the 141575 patent Oxazine from i-anilido-2 · 4-dioxyanthraquinone.
50 kg Purpurin und 5 kg Borsäure werden in 300 kg Nitrobenzol bei 160 bis 2200 gelöst. In die heiße Schmelze werden sodann unter Umrühren 60 kg p-Toluidin allmählich und in kleinen Anteilen eingetragen und so lange auf die angegebene Temperatur erhitzt, bis keine Zunahme an Oxazin mehr wahrnehmbar ist. Man läßt die Schmelze erkalten, wobei sich das Oxazin (identisch mit dem Körper aus 1 · p-Toluido-2 · 4-dioxyanthrachinon der Patentschrift 1415 75) kristallisiert abscheidet.Purpurin 50 kg and 5 kg of boric acid are dissolved in 300 kg of nitrobenzene at 160 to 220 0th 60 kg of p-toluidine are then gradually added in small portions to the hot melt with stirring and heated to the specified temperature until no increase in oxazine is perceptible. The melt is allowed to cool, and the oxazine (identical to the body of 1 · p-toluido-2 · 4-dioxyanthraquinone from Patent 141575) precipitates in crystallized form.
50 kg Purpurin werden in 300 kg Nitrobenzol bei 160 bis 22o° gelöst, 10 kg Eisenoxyd, sodann allmählich 5 kg Borsäure eingetragen. In die heiße Schmelze werden sodann unter Umrühren 60 kg ρ-Toluidin allmählich und in kleinen. Anteilen eingetragen und so lange auf die angegebene Temperatur erhitzt, bis keine Zunahme an Oxazin mehr wahrnehmbar ist. Man läßt erkalten, wobei sich das Oxazin, identisch mit dem Körper des Beispiels 2, kristallisiert abscheidet. Durch Lösen in heißem Anilin und Filtration wird das Oxazin rein erhalten.50 kg of purpurin are dissolved in 300 kg of nitrobenzene at 160 to 220 °, 10 kg of iron oxide, then gradually introduced 5 kg of boric acid. Then in the hot melt while stirring 60 kg of ρ-toluidine gradually and in small amounts. Registered shares and heated to the specified temperature until there is no more increase in oxazine is perceptible. It is allowed to cool, whereby the oxazine is identical to the body of Example 2, precipitated in crystallized form. By dissolving in hot aniline and filtering it becomes keep the oxazine pure.
In analoger Weise verläuft die Reaktion, wenn man die in obigen Beispielen verwendeten Amine durch analoge oder homologe primäre aromatische Amine ersetzt.The reaction proceeds in an analogous manner if the examples above are used Amines replaced by analogous or homologous primary aromatic amines.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE153770C true DE153770C (en) |
Family
ID=420367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT153770D Active DE153770C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE153770C (en) |
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0
- DE DENDAT153770D patent/DE153770C/de active Active
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