DE249721C - - Google Patents
Info
- Publication number
- DE249721C DE249721C DENDAT249721D DE249721DA DE249721C DE 249721 C DE249721 C DE 249721C DE NDAT249721 D DENDAT249721 D DE NDAT249721D DE 249721D A DE249721D A DE 249721DA DE 249721 C DE249721 C DE 249721C
- Authority
- DE
- Germany
- Prior art keywords
- sulfuric acid
- nitrating
- acid
- yellow
- dichloroanthraquinone
- 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
- 230000000802 nitrating Effects 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- -1 z. B. Anthrarufin Chemical class 0.000 description 2
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical class C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 Acetic Acid Drugs 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- JPICKYUTICNNNJ-UHFFFAOYSA-N anthrarufin Chemical compound O=C1C2=C(O)C=CC=C2C(=O)C2=C1C=CC=C2O JPICKYUTICNNNJ-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
-M 249721 KLASSE 12 o. GRUPPE -M 249721 CLASS 12 or GROUP
Patentiert im Deutschen Reiche vom 2. Juni 1911 ab.Patented in the German Empire on June 2, 1911.
In der Patentschrift 137782 wurde beschrieben, daß man durch Nitrierung der α-α-Dihalogenanthrachinone
zu den entsprechenden p-Dinitrohalogenanthrachinonen gelangt.
Es wurde nun gefunden, daß man wohlcharakterisierte ρ - Mononitroverbindungen erhält,
wenn man die einem Molekül Salpetersäure entsprechende Menge Nitriersäure zur Einwirkung
bringt, oder auch, wenn man bei Anwendung überschüssiger Nitriersäure die Reaktion
vor Beginn der Dinitrierung abbricht. Dieses Resultat war nicht vorauszusehen, da bei analog konstituierten Anthrachinonderivaten,
wie z. B. Anthrarufin, den Diaminoanthrachinonen usw., bei gemäßigter Nitrierung
nur Gemische der Dinitrokörper mit unverändertem Ausgangsmaterial entstehen, während
bei dem vorliegenden Verfahren Dinitroverbindungen gar nicht oder nur in ganz untergeordneter Menge sich bilden.In patent 137782 it was described that the corresponding p-dinitrohaloanthraquinones are obtained by nitration of the α-α-dihaloanthraquinones.
It has now been found that well-characterized ρ-mononitro compounds are obtained if the amount of nitrating acid corresponding to one molecule of nitric acid is applied, or if, when using excess nitrating acid, the reaction is terminated before the start of the dinitration. This result could not be foreseen, since with analogously constituted anthraquinone derivatives, such as z. B. Anthrarufin, the diaminoanthraquinones, etc., with moderate nitration only mixtures of dinitro bodies with unchanged starting material are formed, while in the present process dinitro compounds do not form at all or only in a very minor amount.
Die neuen Monomtrodihalogenanthrachinone bilden wertvolle Ausgangsmaterialien zur Darstellung von Farbstoffen, indem sie z. B. mit Aminen kondensiert oder reduziert werden.The new monomtrodihalogenanthraquinones form valuable starting materials for preparation of dyes by e.g. B. condensed or reduced with amines.
20 kg i- 5-Dichloranthrachinon, welche in 400 kg Schwefelsäuremonohydrat gelöst sind, werden bei 40 bis 500 mit 23 1 Nitriersäure (200 g HNO3 im Liter), entsprechend ι Molekül, versetzt. Nach einigen Stunden wird das Gemisch in Eiswasser gegossen, der Nitrokörper abgesaugt und neutral gewaschen. Durch fraktionierte Kristallisation aus Nitrobenzol oder Eisessig wird die erheblich leichter lösliche Mononitroverbindung von der in geringer Menge nebenher entstandenen Dini-"troverbindung getrennt. Das ι · 5-Dichlor-4-nitroanthrachinon kristallisiert in gelben Nadeln, die sich in organischen Lösungen mit schwach gelber, in konzentrierter Schwefelsäure mit gelber Farbe lösen.20 kg of i- 5-dichloroanthraquinone, which are dissolved in 400 kg of sulfuric acid monohydrate, are mixed at 40 to 50 ° with 23 l of nitrating acid (200 g of HNO 3 per liter), corresponding to ι molecule. After a few hours, the mixture is poured into ice water, the nitro body is filtered off with suction and washed neutral. By fractional crystallization from nitrobenzene or glacial acetic acid, the considerably more easily soluble mononitro compound is separated from the dinitro compound which is also formed in small amounts. dissolve in concentrated sulfuric acid with yellow color.
Aus ι · 8-Dichloranthrachinon erhält man auf die gleiche Weise das 1 · 8-Dichlor-4-nitroanthrachinon. Es bildet aus Nitrobenzol kristallisiert bernsteingelbe Prismen, die sich in organischen Solventien mit gelblicher, in konzentrierter Schwefelsäure ziemlich schwer mit gelber Farbe lösen.From ι · 8-dichloroanthraquinone is obtained in the same way the 1x8-dichloro-4-nitroanthraquinone. It forms crystallized from nitrobenzene Amber-yellow prisms, which are yellowish in organic solvents, in concentrated Sulfuric acid quite difficult to dissolve with yellow color.
Zu einer Lösung von 20 kg 1 · 8-Dichloranthrachinon in 300 kg Schwefelsäure von 66° Be. werden bei 200 ziemlich rasch 45 1 Nitriersäure (200 g HNO3 pro Liter), = 2 Molekülen, zugesetzt. Sobald die Abscheidung des Nitrokörpers beendet erscheint, was nach etwa V2 Stunde der Fall zu sein pflegt, wird dieser auf einem Asbestfilter abgesaugt und ausgewaschen. Er stellt nahezu reines 1 · 8-Dichlor-4-nitroanthrachinon dar.To a solution of 20 kg of 1 · 8-dichloroanthraquinone in 300 kg of sulfuric acid of 66 ° Be. are grown at 20 0 45 1 rather quickly nitrating acid (200 g HNO 3 per liter) = 2 molecules added. As soon as the deposition of the nitro body appears to have ended, which is usually the case after about two and a half hours, it is sucked off on an asbestos filter and washed out. It is almost pure 1 · 8-dichloro-4-nitroanthraquinone.
Analog den Chloranthrachinonen verhalten sich die entsprechenden Bromverbindungen.The corresponding bromine compounds behave analogously to the chloranthraquinones.
Beispiel 3. g Example 3. g
Eine Lösung von 20 kg 1 · 5-Dibromanthrachinon in 400 kg Schwefelsäuremonohydrat wird bei 40 bis 500 mit 17 1 Nitriersäure (200 g HNO3 im Liter), entsprechend 1 Molekül, versetzt. Der Nitrokörper wird wie inA solution of 20 kg 1 x 5-dibromoanthraquinone in 400 kg of sulfuric acid monohydrate is (200 g HNO 3 per liter) at 40 to 50 0 to 17 1 nitrating corresponding to 1 molecule are added. The nitro body becomes like in
Beispiel i angegeben isoliert und gereinigt.Example i indicated isolated and purified.
Das ι ■ 5-Dibrom-4-nitroanthrächinon bildet aus Nitrobenzol kristallisiert gelbe Nadeln, die in konzentrierter Schwefelsäure kaum löslieh, in Schwefelsäuremonohydrat gelb, in Oleum von 20 Prozent orangefarben löslich sind.The ι ■ 5-dibromo-4-nitroanthraquinone forms yellow needles crystallize from nitrobenzene, which are hardly soluble in concentrated sulfuric acid, yellow in sulfuric acid monohydrate, soluble in oleum of 20 percent orange are.
An Stelle der Schwefelsäure können auchInstead of sulfuric acid you can also use
andere geeignete Verdünnungsmittel verwendet werden.other suitable diluents can be used.
Claims (1)
Verfahren zur Darstellung von p-Mononitrodihalogenanthrachinonen, darin bestehend, daß man 1 · 5- bzw. 1 · 8-Dihalogenanthrachinone mit der zur Einführung einer Nitrogruppe erforderlichen Menge eines nitrierenden Mittels behandelt, oder daß man bei Anwendung eines Überschusses des nitrierenden Mittels die Einwirkung unterbricht, bevor die Dinitrierung eintritt.Patent claim:
A process for the preparation of p-mononitrodihaloanthraquinones, consisting in treating 1 × 5- or 1 × 8-dihaloanthraquinones with the amount of a nitrating agent required to introduce a nitro group, or if an excess of the nitrating agent is used, the action is interrupted before dinitration occurs.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE249721C true DE249721C (en) |
Family
ID=508315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT249721D Active DE249721C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE249721C (en) |
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0
- DE DENDAT249721D patent/DE249721C/de active Active
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