AT34571B - Process for the preparation of dyes of the thioindigo series. - Google Patents
Process for the preparation of dyes of the thioindigo series.Info
- Publication number
- AT34571B AT34571B AT34571DA AT34571B AT 34571 B AT34571 B AT 34571B AT 34571D A AT34571D A AT 34571DA AT 34571 B AT34571 B AT 34571B
- Authority
- AT
- Austria
- Prior art keywords
- dyes
- thioindigo
- preparation
- thioindigo series
- aromatic
- Prior art date
Links
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 title claims description 10
- 239000000975 dye Substances 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 aromatic nitro hydrocarbons Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical class OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IQZPDFORWZTSKT-UHFFFAOYSA-N nitrosulphonic acid Chemical class OS(=O)(=O)[N+]([O-])=O IQZPDFORWZTSKT-UHFFFAOYSA-N 0.000 description 1
- ZFDMVEOVDOINLW-UHFFFAOYSA-M potassium;2-nitrobenzenesulfonate Chemical compound [K+].[O-][N+](=O)C1=CC=CC=C1S([O-])(=O)=O ZFDMVEOVDOINLW-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Coloring (AREA)
- Indole Compounds (AREA)
Description
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Verfahren zur Darstellung von Farbstoffen der Thioindigoreihe.
Nach dem Verfahren des D. R. P. Nr. 187586 vom 5. November 1905 erhält man Thioindigo durch Erhitzen von Thiosalizylessigsäure mit aromatischen Nitrokohlenwasserstoffen, z. B. Nitrobenzol, auf die Siedetemperatur der letzteren. Der Verlauf dieser Reaktion ist dahin aufzufassen, dass die Thiosalizylessigsäure bei der Siedetemperatur des Nitrobenzols unter Wasser und Kohlensäureabspaltung zunächst in x-Oxythionaphten übergeht, welch letzteres durch das siedende Nitrobenzol zu Thioindigo oxydiert wird.
Versuche haben nun ergeben, dass die Sulfosäuren der aromatischen Nitrokohlenwasserstoffe die α-Oxythionaphtene in wässrig-alkalischen Lösungen nicht zu den entsprechenden Thioindigofarbstoffen zu oxydieren vermögen. Versetzt man z. B. eine ätzalkalische Lösung von x-Oxythionaphten mit der Lösung eines nitrobenzolsulfosauren Salzes, so tritt bei Luftabschluss keine Veränderung ein. während an der Luft langsam kleine Mengen Thioindigo abgeschieden werden, nicht mehr und nicht weniger als unter gleichen Bedingungen aus einer reinen, alkalischen oc-Oxythiona phtenlösung.
Es hat sich nun die überraschende Tatsache ergeben, dass die Sulfosäuren der aromatischen Nitrokohlenwasserstoffe die 11-0xythionaphtene in Gegenwart von Schwefelalkalien, z. B. Schwefelnatrium, schon in der Kälte, wie auch in der Wärme, sofort und in guter Ausbeute zu den ent- sprechenden Thioindigofarbstoffcn zu oxydieren vermögen, wobei sich noch der besondere Vorteil ergibt, dass man nicht genötigt ist, bei so hohen Temperaturen zu arbeiten, wie im D. R. P.
Nr. 187586 angegeben ist.
Beispiel : 30 Teile o-Oxythionaphten werden in 100 Teilen Natronlauge von etwa 8% gelöst. Zu dieser Lösung fügt man in beliebiger Reihenfolge oder gemischt eine wässrige Lösung von 30 Teilen kristallisiertem Schwefelnatrium und eine ebensolche von 40 Teilen nitrobenzol- sulfosaurem Kalium. Die Ahscheidung des Thioindigo beginnt alsbald und ist in wenigen Minuten beendet. Der Farbstoff wird auf einem Filter gesammelt, gewaschen und getrocknet.
In obigem Beispiel kann man das Schwefelnatrium durch andere Alkali-oder Erdalkalisulfide, das nitrobenzolsufosaure Salz durch die Salze der Sulfosäuren anderer aromatischer Xitrokohlenw8ssprstoffe ersetzen. Aus dn Farbstofffiltraten kann man in bekannter Weise die den angewandten Nitrosulfosäuren entsprechenden Aminosulfosäuren gewinnen.
Das Verfahren bleibt das gleiche. wenn man an Stelle des in obigem Beispiel genannten α-Oxythionaphtens äquivalente Mengen der bekannten homologen oder substituierten x-Oxythio- naphtene zur Anwendung bringt. Man erhält so die bekannten homologen und substituierten Thioindigofarbstoffe.
**WARNUNG** Ende DESC Feld kannt Anfang CLMS uberlappen**.
<Desc / Clms Page number 1>
Process for the preparation of dyes of the thioindigo series.
According to the procedure of D. R. P. No. 187586 of November 5, 1905, thioindigo is obtained by heating thiosalicyl acetic acid with aromatic nitro hydrocarbons, e.g. B. nitrobenzene, to the boiling point of the latter. The course of this reaction is to be understood as such that the thiosalicyl acetic acid at the boiling point of the nitrobenzene under water and carbonic acid splitting off initially converts into x-oxythionaphthene, which is oxidized to thioindigo by the boiling nitrobenzene.
Experiments have now shown that the sulfonic acids of the aromatic nitrohydrocarbons are unable to oxidize the α-oxythionaphthens in aqueous-alkaline solutions to the corresponding thioindigo dyes. If you move z. B. a caustic solution of x-oxythionaphthene with a solution of a nitrobenzenesulfonic acid salt, so there is no change in the absence of air. while small amounts of thioindigo are slowly deposited in air, no more and no less than under the same conditions from a pure, alkaline oc-Oxythiona phten solution.
The surprising fact has now emerged that the sulfonic acids of the aromatic nitrohydrocarbons give the 11-oxythionaphtenes in the presence of alkaline sulfur, e.g. B. Sodium sulphide, in the cold as well as in the warm, are able to oxidize immediately and in good yield to the corresponding thioindigo dyes, with the particular advantage that there is no need to work at such high temperatures as in the DRP
No. 187586 is indicated.
Example: 30 parts of o-oxythionaphthene are dissolved in 100 parts of about 8% sodium hydroxide solution. An aqueous solution of 30 parts of crystallized sodium sulphide and an equal amount of 40 parts of potassium nitrobenzenesulphonate are added to this solution in any order or mixed. The elimination of thioindigo begins immediately and is completed in a few minutes. The dye is collected on a filter, washed and dried.
In the above example, the sodium sulphide can be replaced by other alkali or alkaline earth sulphides, and the nitrobenzenesulfo acid salt by the salts of the sulphonic acids of other aromatic nitrocarbons. The aminosulfonic acids corresponding to the nitrosulfonic acids used can be obtained from the dye filtrates in a known manner.
The procedure remains the same. if, instead of the α-oxythionaphthene mentioned in the above example, equivalent amounts of the known homologous or substituted x-oxythionaphthene are used. The known homologous and substituted thioindigo dyes are thus obtained.
** WARNING ** End of DESC field may overlap beginning of CLMS **.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT34571T | 1907-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AT34571B true AT34571B (en) | 1908-09-25 |
Family
ID=3550780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AT34571D AT34571B (en) | 1907-06-27 | 1907-06-27 | Process for the preparation of dyes of the thioindigo series. |
Country Status (1)
| Country | Link |
|---|---|
| AT (1) | AT34571B (en) |
-
1907
- 1907-06-27 AT AT34571D patent/AT34571B/en active
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