DE46938C - Process for the preparation of indamines, indophenols and dyes of the safranine and methylene blue group from p-amidophenylpiperidine - Google Patents
Process for the preparation of indamines, indophenols and dyes of the safranine and methylene blue group from p-amidophenylpiperidineInfo
- Publication number
- DE46938C DE46938C DENDAT46938D DE46938DA DE46938C DE 46938 C DE46938 C DE 46938C DE NDAT46938 D DENDAT46938 D DE NDAT46938D DE 46938D A DE46938D A DE 46938DA DE 46938 C DE46938 C DE 46938C
- Authority
- DE
- Germany
- Prior art keywords
- amidophenylpiperidine
- preparation
- solution
- hand
- dye
- 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.)
- Expired - Lifetime
Links
- 239000000975 dye Substances 0.000 title claims description 8
- OARRHUQTFTUEOS-UHFFFAOYSA-N Safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 title description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- 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 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-Naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N Dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001045 blue dye Substances 0.000 claims description 2
- MIMJFNVDBPUTPB-UHFFFAOYSA-N potassium hexacyanoferrate(3-) Chemical compound [K+].[K+].[K+].N#C[Fe-3](C#N)(C#N)(C#N)(C#N)C#N MIMJFNVDBPUTPB-UHFFFAOYSA-N 0.000 claims description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M Methylene blue Chemical group [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims 1
- 238000007865 diluting Methods 0.000 claims 1
- 230000001264 neutralization Effects 0.000 claims 1
- 230000001590 oxidative Effects 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- 238000009877 rendering Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RSAZYXZUJROYKR-UHFFFAOYSA-N Indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N Potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229940042115 Methylene blue Drugs 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940069002 Potassium Dichromate Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- LFRHSILXVWWAKJ-UHFFFAOYSA-N N,N-dimethylaniline;hypochlorous acid Chemical compound ClO.CN(C)C1=CC=CC=C1 LFRHSILXVWWAKJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- -1 dimethylaniline amine Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 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
- C09B57/00—Other synthetic dyes of known constitution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Die Erfindung beruht auf der Beobachtung, dafs das durch Reduction des ρ - Nitrophenylpiperidins erhaltene ρ - Amidophenylpiperidin (Ber. d. d. eh. Ges. XX, 680) sich in vielen Beziehungen dem p-Amidodimethylanilin ähnlich verhält.The invention is based on the observation that this is achieved by reducing the ρ-nitrophenylpiperidine obtained ρ - amidophenylpiperidine (Ber. d. d. eh. Ges. XX, 680) is found in many Relationships behave similarly to p-amidodimethylaniline.
Insbesondere gestattet es wie dieses die Darstellung von Indaminen und Indophenolen durch gemeinsame Oxydation mit Aminen und Phenolen. Die so erhaltenen Indamine lassen sich ihrerseits wieder nach bekannter Methode in Safranine überführen. Durch Behandlung mit Oxydationsmitteln in Gegenwart von Schwefelwasserstoff oder Thiosulfaten entstehen schwefelhaltige Derivate aus der Methylenblau-Gruppe. In particular, like this one, it allows the representation of indamines and indophenols by joint oxidation with amines and phenols. Leave the indamines thus obtained convert themselves back into Safranine using a known method. Through treatment with oxidizing agents in the presence of hydrogen sulfide or thiosulfates sulfur-containing derivatives from the methylene blue group.
In nachstendem wird zunächst die Darstellung der durch gemeinsame Oxydation des p-Amidophenylpiperidins mit Anilin, o-Toluidin, Dimethylanilin, α- und β-Naphtol sich bildenden Indamine bezw. Indophenole, sowie die Anwendung der genannten Piperidinbase zur Darstellung von safranin- und methylenblauähnlichen Farbstoffen beschrieben.In the following, the representation of the joint oxidation of p-amidophenylpiperidine will first be presented with aniline, o-toluidine, dimethylaniline, α- and β-naphtol Indamine respectively Indophenols, as well as the use of said piperidine base for the representation described by dyes similar to safranine and methylene blue.
I. Indamine.I. Indamine.
In eine kalte Lösung von 10 kg salzsaurem p-Amidophenylpiperidin und 4,85 kg salzsaurem Anilin in 1 500 1 Wasser läfst man langsam unter Umrühren eine Lösung von 7,38 kg Kaliumbichromat einfliefsen, wobei die anfangs auftretende Rothfärbung bald in einen grün bis blauen Ton umschlägt. Auf Zusatz von Chlorzink und Kochsalz scheidet sich dann das Indamin als blaugrüner Niederschlag ab. Dasselbe ist leicht veränderlich und läfst sich nicht in trockenem Zustande aufbewahren.In a cold solution of 10 kg of hydrochloric acid p-Amidophenylpiperidine and 4.85 kg of hydrochloric aniline in 1,500 liters of water are allowed to run slowly Flow in a solution of 7.38 kg of potassium dichromate while stirring, the red color that initially appears soon turning into a green to blue tone changes. The indamine then separates on the addition of zinc chloride and common salt as a blue-green precipitate. The same thing is easily changeable and does not work Store in a dry condition.
Aehnliche Indamine erhält man, wenn man in obiger Vorschrift das salzsaure Anilin durch 5,35 kg o-Toluidin- oder 5,8 kg Dimethylanilinchlorhydrat ersetzt. Das Dimethylanilinindamin scheidet sich als kupferglänzende Masse ab, welche beim Trocknen matt und glanzlos wird.Similar indamines are obtained if the hydrochloric aniline is used in the above procedure 5.35 kg of o-toluidine or 5.8 kg of dimethylaniline chlorohydrate replaced. The dimethylaniline amine Separates out as a shiny copper mass, which becomes matt and dull when it dries.
II. Indophenole.II. Indophenols.
Zur Darstellung eines Indophenols aus a-Naphtol mischt man 5,4 kg a- Naphtol, gelöst in überschüssiger verdünnter Natronlauge, mit einer 0,5 procent. wässerigen Lösung von 10 kg salzsaurem p-Amidophenylpiperidin und läfst langsam unter Umrühren zu der alkalischen Flüssigkeit 49,3 kg Ferricyankalium, gelöst in Wasser, hinzufliefsen, wobei sofort die Abscheidung des blauen Indophenols erfolgt. Nach beendigter Oxydation übersättigt man schwach mit Salzsäure, filtrirt den dadurch bräunlich gewordenen flockigen Niederschlag ab und wäscht ihn anhaltend bis zur Entfernung der anhaftenden Säure mit Wasser, schliefslich unter Zusatz von etwas Ammoniak. Hierbei nimmt der Farbstoff seine ursprüngliche blaue Farbe wieder an. Im trockenen Zustande zeigt das Indophenol schwachen Kupferglanz und löst sich mit blauer Farbe in Alkohol und Essigsäure.To prepare an indophenol from a-naphtol, 5.4 kg of a- naphtol, dissolved in excess dilute sodium hydroxide solution, are mixed with a 0.5 percent. aqueous solution of 10 kg of hydrochloric acid p-amidophenylpiperidine and slowly let 49.3 kg of potassium ferricyanide, dissolved in water, flow into the alkaline liquid with stirring, the blue indophenol being separated out immediately. When the oxidation is complete, it is slightly oversaturated with hydrochloric acid, the flaky precipitate which has become brownish is filtered off and it is washed continuously with water until the adhering acid is removed, finally with the addition of a little ammonia. The dye takes on its original blue color again. In the dry state the indophenol shows a weak copper luster, and dissolves in alcohol and acetic acid with a blue color.
In ganz analoger Weise erhält man ein Indophenol aus ,6-Naphtol. Dasselbe ist in Alkalien bedeutend leichter löslich als die α-VerbindungAn indophenol is obtained from 6-naphtol in a completely analogous manner. The same is in alkalis significantly more soluble than the α-compound
und liefert mehr rothstichige Lösungen in Alkohol und Essigsäure.and gives more reddish-tinged solutions in alcohol and acetic acid.
Beide Indophenole lassen sich auch in schwach essigsaurer Lösung durch Oxydation mit Eisenchlorid gewinnen.Both indophenols can also be dissolved in a weakly acetic acid solution by oxidation with iron chloride to win.
III. Piperidinsafranin.III. Piperidine saffranine.
Zur Darstellung eines Farbstoffes aus der Safraningruppe werden ι ο kg ρ - Amidophenylpiperidin in 20 kg Salzsäure von 32 pCt und' 2 000 1 Wasser gelöst- und vermischt mit einer Lösung von 11,5 kg Anilin, 50 kg Essigsäure (von 20 pCt.) und 600 1 Wasser.To represent a dye from the saffranine group, ι ο kg ρ - amidophenylpiperidine dissolved in 20 kg hydrochloric acid of 32 pCt and 2,000 liters of water and mixed with one Solution of 11.5 kg of aniline, 50 kg of acetic acid (of 20 pCt.) And 600 liters of water.
Man läfst darauf bei ungefähr 50 C. 25 kg Kaliumbichromat, gelöst in 400 1 Wasser, einlaufen. Nach 24 stündigem Stehen wird die Mischung aufgekocht, filtrirt, der Farbstoff durch Kochsalz gefällt, abfiltrirt und durch Umlösen in siedendem Wasser, Filtriren und Aussalzen weiter gereinigt.One läfst thereon at about 5 0 C. 25 kg of potassium dichromate, dissolved in 400 1 of water, enter. After standing for 24 hours, the mixture is boiled, filtered, the dye is precipitated with common salt, filtered off, and further purified by dissolving in boiling water, filtering and salting out.
Dieses Safranin färbt bläulich-rothe Nuancen.This Safranin has bluish-red shades.
IV. Piperidinblau.IV. Piperidine Blue.
Dieser dem Methylenblau analoge Farbstoff wird erhalten, wenn man eine wässerige Lösung von 10 kg salzsaurem ρ - Amidophenylpiperidin mit Salzsäure stark ansäuert, eine Lösung von 6,4 kg Schwefelwasserstoff in Wasser zufügt und dann unter Umrühren eine Lösung von 20 kg Eisenchlorid zufliefsen läfst. Der blaue Farbstoff wird mit Kochsalz und Chlorzink gefällt, filtrirt und durch Umlösen in Wasser und Fällen mit Kochsalz und Chlorzink weiter gereinigt. Er färbt ähnlich wie Methylenblau, aber grünstichiger.This dye, which is analogous to methylene blue, is obtained by using an aqueous solution of 10 kg of hydrochloric acid ρ - amidophenylpiperidine strongly acidified with hydrochloric acid, a solution of 6.4 kg of hydrogen sulfide in water are added and then a solution of 20 kg of ferric chloride flows in. The blue dye is made with table salt and zinc chloride precipitated, filtered, and further by dissolving in water and precipitating with common salt and zinc chloride cleaned. It has a similar color to methylene blue, but has a more greenish tinge.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE46938C true DE46938C (en) |
Family
ID=322012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT46938D Expired - Lifetime DE46938C (en) | Process for the preparation of indamines, indophenols and dyes of the safranine and methylene blue group from p-amidophenylpiperidine |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE46938C (en) |
-
0
- DE DENDAT46938D patent/DE46938C/en not_active Expired - Lifetime
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