DE46805A - Innovations in the process of preparing sulfur derivatives of paradiamines and converting them into sulfur-containing dyes - Google Patents
Innovations in the process of preparing sulfur derivatives of paradiamines and converting them into sulfur-containing dyesInfo
- Publication number
- DE46805A DE46805A DE1888B8343 DEB8343 DE46805A DE 46805 A DE46805 A DE 46805A DE 1888B8343 DE1888B8343 DE 1888B8343 DE B8343 DEB8343 DE B8343 DE 46805 A DE46805 A DE 46805A
- Authority
- DE
- Germany
- Prior art keywords
- sulfur
- methylene blue
- preparing
- dimethylphenylene
- cold
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims 3
- 239000011593 sulfur Substances 0.000 title claims 3
- 229910052717 sulfur Inorganic materials 0.000 title claims 3
- 239000000975 dye Substances 0.000 title 1
- 150000003463 sulfur Chemical class 0.000 title 1
- 239000000243 solution Substances 0.000 claims description 8
- 229940042115 Methylene blue Drugs 0.000 claims description 7
- KMUONIBRACKNSN-UHFFFAOYSA-N Potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-N-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 229940069002 Potassium Dichromate Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000001264 neutralization Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims 2
- -1 dimethylphenylene Chemical group 0.000 claims 2
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M Methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- JLTDJTHDQAWBAV-UHFFFAOYSA-N Dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QTWZICCBKBYHDM-UHFFFAOYSA-N hydromethylthionine Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- LGDPTPLJZGPOJL-UHFFFAOYSA-N N,N-dimethyl-2-nitrosoaniline Chemical compound CN(C)C1=CC=CC=C1N=O LGDPTPLJZGPOJL-UHFFFAOYSA-N 0.000 description 1
- ZXYNGLRGFYLTQZ-UHFFFAOYSA-M [Zn]Cl Chemical compound [Zn]Cl ZXYNGLRGFYLTQZ-UHFFFAOYSA-M 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000005429 turbidity Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Behandelt man ein Gemisch gleicher Molecule Dimethylanilin und Amidodimethylanilinmer-If a mixture of the same molecules of dimethylaniline and amidodimethylaniline mer-
NH [] NH []
captansulfosäure,captansulfonic acid,
NH2 [i] NH 2 [i]
N(CHJ2 [4], mit
S- SO3H [2]
Oxydationsmitteln, so entsteht ein schwefelhaltiges Indamin, welches sich unter geeigneten
Bedingungen direct in Methylenblau überführen läfst. N (CHJ 2 [4], with S- SO 3 H [2]
Oxidizing agents, a sulphurous indamine is formed which, under suitable conditions, can be converted directly into methylene blue.
Dieses Indamin ist in kaltem Wasser fast vollkommen unlöslich und scheidet sich schon während der Oxydation ab, in der Regel sogleich in Form messinggelber glänzender Nadeln. Seine Zusammensetzung entspricht der Formel:This indamine is almost completely insoluble in cold water and is already separating during the oxidation, usually immediately in the form of shiny brass-yellow needles. Its composition corresponds to the formula:
C16 H19 NB S2. O3 + V2 aq.C 16 H 19 N B S 2 . O 3 + V 2 aq.
Kocht man die reine Verbindung einige Stunden mit Wasser, so wandelt sie sich in einen schmutzig bläulichen Niederschlag um. Versetzt man dann die Flüssigkeit mit verdünnter Schwefelsäure, so löst sich der Niederschlag; die Lösung ist verhältnifsmäfsig wenig gefärbt und enthält Leukomethylenblau, welches sich durch erneuten Zusatz eines Oxydationsmittels in Methylenblau überführen läfst.If you boil the pure compound with water for a few hours, it changes into a dirty bluish precipitate. Then the liquid is mixed with diluted Sulfuric acid, the precipitate dissolves; the solution is comparatively little colored and contains leucomethylene blue, which is changed by adding an oxidizing agent again can be converted into methylene blue.
Kocht man dagegen das schwefelhaltige Indamin mit einer concentrirten Chlorzinklösung, so tritt fast sofort eine reichliche Bildung von Methylenblau ein, und dieser Farbstoff scheidet sich aus der heifsen Flüssigkeit in den glänzenden Nadeln seiner Chlorzinkdoppelverbindung ab. Die daneben entstehende Leukoverbindung des schwefelhaltigen Indamins setzt sich bei längerem Kochen mit dem Methylenblau zu Leukomethylenblau um und kann dann durch eine entsprechende Nachoxydation in den Farbstoff übergeführt werden. Zweckmäfsig vereinigt man aber diese Vorgänge zu einer Operation, indem man der Chlorzinklösung von vornherein noch etwa die Hälfte des zur Indaminbildung erforderlich gewesenen Oxydationsmittels zusetzt.If, on the other hand, the sulphurous indamine is boiled with a concentrated zinc chloride solution, thus an abundant formation of methylene blue occurs almost immediately, and this dye is separated from the hot liquid in the shiny needles of its zinc chloride compound away. The leuco compound of the sulphurous indamine which is formed next to it is added Long boiling with the methylene blue to leucomethylene blue and then cooked through a corresponding post-oxidation can be converted into the dye. Appropriately united but one can convert these processes into an operation by adding about half of the amount to the zinc chloride solution from the start Indamine formation adds oxidizing agent that has been necessary.
Die Ausführung des Verfahrens erläutert nachstehendes Beispiel:The following example explains how to carry out the procedure:
Die aus 6 kg Dimethylanilin durch Ueberführen in salzsaures Nitrosodimethylanilin und Reduction mittelst Zinkstaubs dargestellte Lösung von salzsaurem p-Amidodimethylanilin (ca. 250 1) wird bei 18 bis 200 mit Natronlauge bis zur ersten bleibenden Trübung neutralisirt.Consisting of 6 kg dimethylaniline by conversion into muriate nitrosodimethylaniline and reduction with zinc dust illustrated solution of hydrochloric acid p-Amidodimethylanilin (about 250 1) is neutralized at 18 to 20 0 with sodium hydroxide solution to the first permanent turbidity.
Man setzt dann 16 kg schwefelsaure Thonerde hinzu und läfst nach halbstündigem Rühren eine concentrirte Lösung von 13 kg unterschwefligsaurem Natron und darauf 4,8 kg Kaliumbichromat (gelöst in 75 1 Wasser) schnell einfliefsen.You then add 16 kg of sulfuric alumina and run after half an hour Stir a concentrated solution of 13 kg of hyposulphurous soda and then 4.8 kg Quickly pour in potassium dichromate (dissolved in 75 liters of water).
Zur Vervollständigung der Bildung der p-Amidodimethylanilinmercaptansulfonsäure wird die Mischung während einer Stunde gerührt. Man verdünnt dieselbe dann auf 600 1 und fügt 6 kg Dimethylanilin in Form seines neutralen salzsauren Salzes hinzu.To complete the formation of p-amidodimethylaniline mercaptan sulfonic acid the mixture is stirred for one hour. It is then diluted to 600 l and adds 6 kg of dimethylaniline in the form of its neutral hydrochloric acid salt.
Zur Darstellung des Indamins läfst man nun unter fortwährendem Umrühren bei einer Temperatur von 10 bis 120 C. eine gesättigte Lösung von 14 kg Kaliumbichromat schnell einlaufen, setzt dann 75 kg einer Chlorzink-To illustrate the Indamins one now läfst with constant stirring at a temperature of 10 to 12 0 C. enter quickly a saturated solution of 14 kg of potassium bichromate, then sets a 75 kg Chlorzink-
lösung von 500 B. zu und erhitzt während einer halben Stunde auf ioo° C. Nach dem Erkalten wird das in kristallinischer Form ausgeschiedene Methylenblau filtrit und wie üblich durch Umlösen gereinigt.solution of 50 0 B. and heated for half an hour to 100 ° C. After cooling, the precipitated methylene blue in crystalline form is filtered and purified as usual by dissolving.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE46805A true DE46805A (en) |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3309726C1 (en) | Process for the production of acidic, low-electrolyte dyes of the triphenylmethane series | |
| DE46805A (en) | Innovations in the process of preparing sulfur derivatives of paradiamines and converting them into sulfur-containing dyes | |
| DE2156648B2 (en) | Process for the preparation of 2- [4,4'-bis (dimethylamino) benzohydryl] -5-dimethylaminobenzoic acid | |
| DE71665C (en) | Process for the preparation of an indulin alkylated on the azine nitrogen and a sulphonic acid of the same | |
| DE260899C (en) | ||
| DE281176C (en) | ||
| DE77120C (en) | Process for the preparation of blue stain-coloring oxazine dyes ^ | |
| DE901175C (en) | Process for replacing the diazo group with hydrogen | |
| DE462041C (en) | Process for the production of ªÏ-methylsulfonic acids from diaminoanthraquinones | |
| AT216671B (en) | Process for the preparation of compounds of various penicillins with sulfonamides | |
| DE172929C (en) | ||
| DE265727C (en) | ||
| DE19266C (en) | Innovations in the process for displaying the artificial indigo | |
| AT140567B (en) | Process for removing iron from acidic aluminum salt solutions. | |
| DE146655C (en) | ||
| DE9569C (en) | Process for the production of green dyes by treating the sulfoderivatives of dibenzylaniline, dibenzyltoluidine and benzyldiphenylamine with oxidizing agents | |
| DE222195C (en) | ||
| DE175593C (en) | ||
| DE97638C (en) | ||
| DE186882C (en) | ||
| DE2433889C2 (en) | Process for the production of pure allcls-cyclopentane-1,2,3,4-tetracarboxylic acid or its salts | |
| DE207465C (en) | ||
| DE88084C (en) | ||
| DE62574C (en) | Process for the preparation of new red basic dyes of the triphenylmethane] series | |
| DE77315C (en) |