DE78924C - Process for the preparation of mononitrosodimethylamidocresol - Google Patents
Process for the preparation of mononitrosodimethylamidocresolInfo
- Publication number
- DE78924C DE78924C DENDAT78924D DE78924DA DE78924C DE 78924 C DE78924 C DE 78924C DE NDAT78924 D DENDAT78924 D DE NDAT78924D DE 78924D A DE78924D A DE 78924DA DE 78924 C DE78924 C DE 78924C
- Authority
- DE
- Germany
- Prior art keywords
- dimethyl
- nitrite
- acid
- cresol
- amidocresol
- 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
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 3
- 229960003116 Amyl Nitrite Drugs 0.000 claims description 5
- CSDTZUBPSYWZDX-UHFFFAOYSA-N Amyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 150000002832 nitroso derivatives Chemical class 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009114 investigational therapy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N n-pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Aus Dimethyl- und Diäthyl-m-amidophenol entsteht nach den Angaben der Patentschrift Nr. 45268 beim Nitrosiren in saurer Lösung ein Mononitrosoderivat.From dimethyl- and diethyl-m-amidophenol According to the information in patent specification no. 45268, when nitrosiring occurs in acidic solution a mononitroso derivative.
Die Untersuchung des Dimethylamido-pkresols nach dieser Richtung hin hat ab- -weichende und überraschende Resultate zu Tage gefördert. Behandelt man dasselbe nämlich nach der üblichen Methode mit Nitrit in wässeriger saurer Lösung, so scheidet sich ganz allmälig beim Stehen ein hellbrauner schwer löslicher krystallinischer Körper aus, der in seinen Eigenschaften total von obigen Nitrosoderivaten der Dialkylamidophenole verschieden ist. Vor allem zeigt er nicht mehr die Doppelnatur eines zugleich basischen und sauren Körpers, sondern löst sich nur noch in Alkalien und nicht mehr in Säuren auf. Aufschlufs über die chemische Natur dieses Körpers gab die Untersuchung der bei der Darstellung desselben erhaltenen Mutterlaugen, in welchen reichliche Mengen Dimethylamin nachgewiesen werden konnten. Der Körper ist danach als ein Derivat des zuerst von Hakansson (Ber. V., S. 1087) erhaltenen Cresorcins aufzufassen und stimmt thatsä'chlich.in allen seinen Eigenschaften mit der aus Cresorcin erhaltenen Dinitroso-Verbindung überein.The investigation of dimethylamido-pcresol in this direction has deviating and surprising results Days promoted. If you treat the same thing according to the usual method with nitrite in aqueous, acidic solution, a light brown one separates very gradually on standing with difficulty soluble crystalline body, which in its properties is totally different from the above nitroso derivatives of the dialkylamidophenols is different. Above all, it no longer shows the dual nature a body that is both basic and acidic, but only dissolves in alkalis and no longer in acids. Gave information about the chemical nature of this body the investigation of the mother liquors obtained in the preparation of the same, in which copious amounts of dimethylamine could be detected. The body is then as a derivative of the cresorcin first obtained from Hakansson (Ber. V., p. 1087) and is actually true in all its properties with the dinitroso compound obtained from cresorcinol match.
Die Reaction zwischen salpetriger Säure und Dimethylamidokresol verläuft also in wässeriger saurer Lösung nach folgendem Schema:The reaction between nitrous acid and dimethylamidocresol thus proceeds in an aqueous manner acidic solution according to the following scheme:
C6 HB (CHJ C 6 H B (CHJ
+ + 22
/OH/OH
= C6H(CH3J-OH + NH(CH3J, + H2 O. ^O= C 6 H (CH 3 J-OH + NH (CH 3 J, + H 2 O. ^ O
Auch bei Anwendung von weniger Nitrit, als obiger Gleichung entspricht, entsteht nur Dinitrosocresorcin.Even when using less nitrite than corresponds to the above equation, only Dinitrosocresorcinol.
Ganz andere Resultate erhält man, wenn man gebundene salpetrige Säure entweder in Form ihrer Verbindungen mit Alkoholradicalen (Aethylnitrit, Amylnitrit) auf Dimethyl-m-amidokresol oder dessen Salze einwirken läfst, oder in Form von Metallnitriten mit den Säuresalzen des Dimethyl-m-amidokresols bei Abwesenheit weiterer Säure in Reaction bringt.Completely different results are obtained if bound nitrous acid is either in Form of their compounds with alcohol radicals (ethyl nitrite, amyl nitrite) on dimethyl-m-amidocresol or allows its salts to act, or in the form of metal nitrites with the acid salts brings the dimethyl-m-amidocresol into reaction in the absence of further acid.
In diesen Fällen findet ein von dem oben geschilderten ganz verschiedener chemischer Vorgang statt. Beispielsweise beobachtet man beim Zusammenbringen alkoholischer Lösungen von Dimethyl-m-amidokresolnatrium mit Amylnitrit Folgendes: Die Flüssigkeit färbt sich ganz allmälig gelb bis gelbbraun, und nach längerem Stehen scheiden sich glänzende schwarzbraune Blätter ab, welche ein Natronsalz darstellen. Dasselbe löst sich in Wasser leicht mit gelbrother Farbe auf, auf Zusatz von Essigsäure entsteht ein rother Niederschlag, welcher sich auf Zusatz von Salzsäure wieder löst, eventuell bei genügender Concentration sich in ein gelbes krystallinisches Pulver eines Chlorhydrats verwandelt. In these cases there is a very different chemical from the one described above Process takes place. For example, one observes when alcoholic solutions are brought together of dimethyl-m-amidocresol sodium with amyl nitrite does the following: The liquid becomes completely colored Gradually yellow to yellow-brown, and after prolonged standing, glossy black-brown separates Leaves off, which are a sodium salt. The same easily dissolves in water with yellowish-red Color on, on addition of acetic acid a red precipitate is formed, which is dissolves again on the addition of hydrochloric acid, possibly turning into a yellow one with sufficient concentration crystalline powder of a chlorohydrate transformed.
Vermischt man die kalten wässerigen neutralen Lösungen von salzsaurem Dimethylm-amidokresol und Natriumnitrit, so beobachtet man zunächst gar keine Einwirkung. Ganz allmälig färbt sich indessen die Flüssigkeit braunroth und scheidet nach und nach einen rothen krystallinischen Körper ab, der sich als identisch mit dem aus obigem Natronsalz mittelst Essigsäure erhaltenen erweist.Mix the cold aqueous neutral solutions of hydrochloric acid dimethylm-amidocresol and sodium nitrite, no action at all is observed at first. The liquid gradually changes color brownish-red and gradually separates a red crystalline body, which turns out to be Identical to that obtained from the above sodium salt by means of acetic acid.
Das derart erhaltene Nitrosoderivat ist dieThe nitroso derivative thus obtained is the
wahre Mononitroso-Verbmdung des Dimethylm-amidokresols. Sie entsteht nach dem oben Gesagten nur unter Innehaltung ganz bestimmter Bedingungen. Der Schmelzpunkt des aus Toluol in glänzenden Nadeln krystallisirten Präparats liegt bei 105° C.true mononitroso compound of dimethylm-amidocresol. According to what has been said above, it only arises under certain conditions. The melting point of the from toluene The preparation crystallized in shiny needles is at 105 ° C.
Beispiele zur Darstellung der Mononitro so-Verbin du ng.Examples of the representation of the Mononitro so-connect you ng.
a) 15 kg Dimethyl-m-amidokresol werden mit 4 kg Aetznatron in 45 1 Spiritus gelöst. Zu der mit Eis gekühlten Lösung werden allmälig 14 kg Amylnitrit zugesetzt. Die Flüssigkeit färbt sich allmälig gelb bis gelbbraun und wird etwa 24 Stunden der Ruhe überlassen. Sie zeigt sich alsdann erfüllt mit grünglänzenden Blättchen des Natriumsalzes der Nitroso-Verbindung. Diese werden abfiltrirt, geprefst und getrocknet.a) 15 kg of dimethyl-m-amidocresol are used with 4 kg of caustic soda dissolved in 45 liters of alcohol. To the solution cooled with ice gradually become 14 kg of amyl nitrite added. The liquid gradually turns yellow to yellow-brown and is left to rest for about 24 hours. It then shows itself filled with shimmering green Leaflets of the sodium salt of the nitroso compound. These are filtered off and pressed and dried.
Statt Amylnitrit läfst sich hierbei auch Aethylnitrit, statt Aethylalkohöl auch z. B. Amylalkohol verwenden. Ferner läfst sich die Reaction auch mit Aetzkali statt Aetznatron bewerkstelligen, ohne dafs indefs dadurch ein Vortheil erreicht wird.Instead of amyl nitrite, ethyl nitrite can also be used, instead of ethyl alcohol also z. B. Use amyl alcohol. Furthermore, the Realize reaction with caustic potash instead of caustic soda, without, however, an advantage being achieved thereby.
b) 1 5 kg Dimethyl-m-amidokresol werden in 10 1 Salzsäure und 50 1 Wasser gelöst und die Lösung unter Eiskühlung allmälig mit einer Lösung von 7,5 kg Natriumnitrit in 1 5 1 Wasser versetzt. Der nach einiger Zeit entstehende rothbraune Brei der Nitroso-Verbindung wird abfiltrirt, ausgewaschen und dann zweckmäfsig in das Chlorhydrat verwandelt.b) 1 5 kg of dimethyl-m-amidocresol are in 10 1 hydrochloric acid and 50 1 water dissolved and the solution gradually with a A solution of 7.5 kg of sodium nitrite in 1 5 1 of water was added. The one that arises after a while The red-brown pulp of the nitroso compound is filtered off, washed out, and then expedient transformed into the chlorohydrate.
Das erhaltene Mononitrosodimethylamidokresol färbt Eisenbeizen lebhaft grün an und dient aufserdem in Combination mit aromatischen Aminen zur Darstellung einer grofsen Anzahl sehr werthvoller Farbstoffe.The mononitrosodimethylamidocresol obtained gives iron stains a vivid green color is also used in combination with aromatic amines to represent a large Number of very valuable dyes.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE78924C true DE78924C (en) |
Family
ID=351608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT78924D Expired - Lifetime DE78924C (en) | Process for the preparation of mononitrosodimethylamidocresol |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE78924C (en) |
-
0
- DE DENDAT78924D patent/DE78924C/en not_active Expired - Lifetime
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