DE107721C - - Google Patents
Info
- Publication number
- DE107721C DE107721C DENDAT107721D DE107721DA DE107721C DE 107721 C DE107721 C DE 107721C DE NDAT107721 D DENDAT107721 D DE NDAT107721D DE 107721D A DE107721D A DE 107721DA DE 107721 C DE107721 C DE 107721C
- Authority
- DE
- Germany
- Prior art keywords
- bromine
- anthraquinone
- solution
- bromanthraquinone
- acid
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- RZVHIXYEVGDQDX-UHFFFAOYSA-N Anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 5
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- MRDPPBWQEBZWKE-UHFFFAOYSA-N 2-benzoyl-3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1C(=O)C1=CC=CC=C1 MRDPPBWQEBZWKE-UHFFFAOYSA-N 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N Anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 210000003298 Dental Enamel Anatomy 0.000 description 1
- 210000002268 Wool Anatomy 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 heptabromanthraquinone Chemical compound 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/02—Hydroxy-anthraquinones; Ethers or esters thereof
- C09B1/06—Preparation from starting materials already containing the anthracene nucleus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE 12: Chemische Verfahren und Apparate.CLASS 12: Chemical processes and apparatus.
Patentirt im Deutschen Reiche vom 18. Oktober 1898 ab.Patented in the German Empire on October 18, 1898.
Bromderivate des Anthrachinons sind bisher erhalten worden durch Oxydation von Bromderivaten des Anthracens, durch Behandlung von Anthrachinon mit Brom bei hoher Temperatur (s. Ber. X, S. 1213, Ber. XI, S. 181) und aus Brombenzoylbenzoesäure (s. Ber. XII, S. 2137).Bromine derivatives of anthraquinone have hitherto been obtained by oxidation of bromine derivatives des anthracene, by treating anthraquinone with bromine at high temperature (see Ber. X, p. 1213, Ber. XI, p. 181) and from bromobenzoylbenzoic acid (see Ber. XII, p. 2137).
Es wurde nun gefunden, dafs man schon bei niedriger Temperatur sehr leicht und glatt zu technisch wichtigen Bromverbindungen gelangt, wenn man Brom auf eine Lösung von Anthrachinon in rauchender Schwefelsäure einwirken läfst. Es ist also auch hier, ähnlich wie in den Verfahren, welche in den Patenten 50177 und 99314 angeführt sind, die Gegenwart von Oleum von günstigem Einflufs auf die Einführung von Brom in schwer halogenisirbare Körper.It has now been found that, even at a low temperature, it is very easy and smooth leads to technically important bromine compounds if you add bromine to a solution of Let anthraquinone act in fuming sulfuric acid. So here, too, it is similar as in the procedures cited in patents 50177 and 99314, the presence of oleum has a favorable influence on the introduction of bromine into those which are difficult to halogenate Body.
Die Darstellung dieser neuen Halogenderivate geschieht im Allgemeinen in der Weise, dafs man Brom langsam in eine Lösung von Anthrachinon in rauchender Schwefelsäure eintropfen läfst. Bei Anwendung von hochprocentiger rauchender Säure beginnt die Reaction schon unter 200 und ist mit einer erheblichen Temperatursteigerung verbunden, bei Anwendung niedrigprocentiger Säure geht die Einwirkung langsam vor sich, und es empfiehlt sich, zum Schlufs die Reaction durch Zufuhr von Wärme zu Ende zu führen.These new halogen derivatives are generally prepared by slowly dripping bromine into a solution of anthraquinone in fuming sulfuric acid. When using hochprocentiger fuming acid, the reaction starts at 20 0, and is connected with a significant increase in temperature, niedrigprocentiger when used acid is the action slow, and it is advisable to lead to the conclusion the reaction by supplying heat to the end.
Man löst 10 kg Anthrachinon in 200 kg rauchender Schwefelsäure ,von 80 pCt. SO3-Gehalt und läfst zu dieser Lösung bei 20 ° unter lebhaftem Umrühren langsam 30 kg Brom einfliefsen, wobei man Sorge trägt, dafs die Temperatur der Schmelze, nicht über 50 bis 60° steigt. Nachdem das Brom eingetragen ist, hält man die Temperatur noch ca. 3 Stunden bei 40 bis 50°, worauf die Reaction beendigt ist. Man verdünnt nun die Schmelze mit Monohydrat und giefst unter den üblichen Vorsichtsmafsregeln auf Eis, wobei sich ein feiner röthlich gefärbter krystallinischer Niederschlag abscheidet, welchen neutral gewaschen und getrocknet wird. Er besteht zum gröfsten Theil aus zwei schwer löslichen Bromanthrachinonen, welche in folgender Weise isolirt werden:10 kg of anthraquinone are dissolved in 200 kg of fuming sulfuric acid, 80 pCt. SO 3 content and 30 kg of bromine slowly flow into this solution at 20 ° with vigorous stirring, taking care that the temperature of the melt does not rise above 50 to 60 °. After the bromine has been added, the temperature is kept at 40 to 50 ° for about 3 hours, after which the reaction is ended. The melt is then diluted with monohydrate and poured onto ice, taking the usual precautionary measures, a fine, reddish-colored crystalline precipitate separating out, which is washed neutral and dried. It consists for the most part of two sparingly soluble bromanthraquinones, which are isolated in the following way:
Man extrahirt zunächst mit Aceton, um leicht lösliche Beimengungen zu entfernen, und behandelt den Rückstand mit 10 Theilen siedendem Nitrobenzol, wobei das leichter lösliche Bromanthrachinon (Bromanthrachinon A) in Lösung geht. Beim Erkalten scheidet es sich aus der NitrobenzoUösung in feinen Krystallen aus. Durch weiteres Umkrystallisiren aus Xylol oder Nitrobenzol erhält man es rein in Form von gelben Nadeln. Eine Brombestimmung ergab 62,17 pCt. Brom, mithin ist der Körper wahrscheinlich ein Tetrabromanthrachinon, welches 6i,o7pCt. Brom verlangt.It is first extracted with acetone, in order to remove easily soluble impurities, and treated the residue with 10 parts of boiling nitrobenzene, the more easily soluble Bromanthraquinone (bromanthraquinone A) goes into solution. When it cools down, it separates from the nitrobenzo solution in fine crystals. By further recrystallization from xylene or nitrobenzene, it is obtained purely in the form of yellow needles. A bromine determination found 62.17 pCt. Bromine, therefore the body is probably a tetrabromanthraquinone, which 6i, o7pCt. Bromine required.
Der in Nitrobenzol ungelöst gebliebene Rückstand enthält das andere Product (Bromanthrachinon B), welches in allen organischen Lösungsmitteln sehr schwer löslich ist, in fast reiner Form. Man erhält es ganz rein durchThe residue that remained undissolved in nitrobenzene contains the other product (bromanthraquinone B), which is very sparingly soluble in all organic solvents, in almost pure form. You get it all through
Unikrystallisiren aus viel Nitrobenzol, aus welchem es sich in feinen gelben Nä'delchen ausscheidet. Eine Brombestimmung ergab hier 72,83 pCt. Brom. Es ist mithin augenscheinlich ein Heptabromanthrachinon, welches 73,58 pCt. Brom verlangt. ·Unicrystallize from a lot of nitrobenzene, from which it is precipitated in fine yellow needles. A bromine determination here resulted in 72.83 pCt. Bromine. It is therefore apparently a heptabromanthraquinone, which 73.58 pCt. Bromine required. ·
Die Eigenschaften der Producte sind aus folgender Tabelle zu ersehen:The properties of the products can be seen from the following table:
punktEnamel
Point
säureSolution in cone. sulfur
acid
in Violettroth übergehendinitially red-brown when boiling
merging into violet red
Erhitzen rothgelbLittle soluble in the cold, when
Heating red-yellow
Kochen erst braunroth, dann
grüninsoluble in the cold, at
Cooking first brown-red, then
green
wenig löslich mit gelber Farbe,in the cold and warm very much
slightly soluble with yellow color,
Die nach obigem Verfahren erhaltenen Bromverbindungen können, wie in dem Patent 107730 ausgeführt ist, zur Darstellung werthvoller Wollfarbstoffe Verwendung finden.The bromine compounds obtained by the above process can, as in patent 107730 is carried out, find use for the representation of valuable wool dyes.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE107721C true DE107721C (en) |
Family
ID=377763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT107721D Active DE107721C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE107721C (en) |
-
0
- DE DENDAT107721D patent/DE107721C/de active Active
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