DE2932460A1 - Bis-2,4-di:aminophenoxy-alkane derivs. - used as developer components in oxidn. hair dyes - Google Patents
Bis-2,4-di:aminophenoxy-alkane derivs. - used as developer components in oxidn. hair dyesInfo
- Publication number
- DE2932460A1 DE2932460A1 DE19792932460 DE2932460A DE2932460A1 DE 2932460 A1 DE2932460 A1 DE 2932460A1 DE 19792932460 DE19792932460 DE 19792932460 DE 2932460 A DE2932460 A DE 2932460A DE 2932460 A1 DE2932460 A1 DE 2932460A1
- Authority
- DE
- Germany
- Prior art keywords
- bis
- diaminophenoxy
- alkane
- stage
- alkanes
- 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.)
- Granted
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
"Verbessertes Verfahren zur Herstellung von Bis-(2,4-"Improved process for the production of bis (2,4-
diaminophenoxy) -alkanen" Gegenstand der Erfindung ist ein verbessertes zweistufiger Verfahren zur Herstellung von Bis-(2,4-diaminophenoxy)-alkanen.diaminophenoxy) alkanes "The invention provides an improved two-step process for the preparation of bis (2,4-diaminophenoxy) alkanes.
Zur Herstellung der Bis-(2,4-diaminophenoxy) -alkane bediente man sich bisher üblicherweise eines vierstufigen Verfahrens, welches über nachstehend aufgeführte Stufen verlief: 1. Stufe: Acetylierung von 2-Amino-4-nitrophenol zu 2-Acetylamino-4-nitrophenol.For the preparation of bis (2,4-diaminophenoxy) alkanes one served So far it has usually been a four-step process, which is about below The stages listed proceeded: 1st stage: Acetylation of 2-amino-4-nitrophenol to 2-acetylamino-4-nitrophenol.
2. Stufe: Umsetzung von 2-Acetylamino-4-nitrophenol mit Dibromalkan zu Bis-(2-acetylamino-4-nitrophenoxy)-alkanen.2nd stage: reaction of 2-acetylamino-4-nitrophenol with dibromoalkane to bis (2-acetylamino-4-nitrophenoxy) alkanes.
3. Stufe: Abspaltung der Acetylgruppen der Bis-(2-acetylamino-4-nitrophenoxy)-alkane durch Kochen mit Salzsäure zu Bis-(2-amino-4-nitrophenoxy)-alkanen.3rd stage: splitting off of the acetyl groups of the bis (2-acetylamino-4-nitrophenoxy) alkanes by boiling with hydrochloric acid to bis (2-amino-4-nitrophenoxy) alkanes.
4. Stufe: Katalytische Reduktion der Bis-(2-amino-4-nitrophenoxy)-alkane zu Bis-(2,4-diaminophenoxy ) -alkanen.4th stage: Catalytic reduction of the bis (2-amino-4-nitrophenoxy) alkanes to bis (2,4-diaminophenoxy) alkanes.
Die Reaktionen der ersten drei Verfahrensstufen werden näher in der deutschen Offenlegungsschrift 2 658 329 beschrieben, während die Reduktion gemäß der vierten Stufe in Anlehnung an literaturbekannte Hydrierverfahren erfolgt. Ein derartiges vierstufiges Herstellungsverfahren ist jedoch sehr aufwendig, so daß der Wunsch nach einem einfacheren Verfahren bestand.The reactions of the first three procedural steps are detailed in the German Offenlegungsschrift 2 658 329, while the reduction according to the fourth stage is carried out on the basis of hydrogenation processes known from the literature. A Such a four-stage manufacturing process is very expensive, so that there was a desire for a simpler procedure.
Es wurde nun ein verbessertes Verfahren zur Herstellung von Bis-(2,4-diaminophenoxy)-alkanen der allgemeinen Formel in der R einen geradkettigen oder verzweigtkettigen Alkylenrest mit 1 - 12 Kohlenstoffatomen darstellt, aufgefunden, bei dem man in erster Stufe 2,4-Dinitrophenolat-anion, hergestellt durch Zugabe einer Base zu 2,4-Dinitrophenol, in einem geeigneten Lösungsmittel mit einem Dibromalkan der Formel Br-R-Br, in der R die vorgenannte Bedeutung besitzt, bei Temperaturen zwischen 80 - 2000 C innerhalb von 1/2 - 12 Stunden umsetzt, das so gebildete Bis-(2,4-dinitrophenoxy)-alkan durch Waschen mit einer Base von 2,4-Dinitrophenol befreit und dieses Bis-(2,4-dinitrophenoxy)-alkan in zweiter Stufe in bekannter Weise durch katalytische Hydrierung in das entsprechende Bis-(2,4-diaminophenoxy)-alkan überführt.There has now been an improved process for the preparation of bis (2,4-diaminophenoxy) alkanes of the general formula in which R represents a straight-chain or branched-chain alkylene radical with 1-12 carbon atoms, found in which in the first stage 2,4-dinitrophenolate anion, prepared by adding a base to 2,4-dinitrophenol, in a suitable solvent with a dibromoalkane of the formula Br-R-Br, in which R has the aforementioned meaning, at temperatures between 80-2000 C within 1/2 - 12 hours, the bis- (2,4-dinitrophenoxy) alkane thus formed is reacted by washing with freed from a base of 2,4-dinitrophenol and this bis (2,4-dinitrophenoxy) alkane is converted in the second stage in a known manner by catalytic hydrogenation into the corresponding bis (2,4-diaminophenoxy) alkane.
Als Basen zur Überführung des 2,4-Dinitrophenols in das 2,4-Dinitrophenolat-anion haben sich Kaliumcarbonat und Kaliumhydroxid am besten bewährt. Geeignete Lösungsmittel für die Durchführung der Reaktion stellen Dimethylformamid, Methylglykol, Diethylenglykolmonomethylether und Diethylenglykoldimethylether dar. Die Umsetzung wird zweckmäßigerweise bei Temperaturen zwischen 100 - 1500 C durchgeführt. Als Katalysator bei der Hydrierung in zweiter Stufe dienen vornehmlich Raney-Nickel oder Palladium auf Kohle.As bases for converting the 2,4-dinitrophenol into the 2,4-dinitrophenolate anion Potassium carbonate and potassium hydroxide have proven to be the best. Suitable solvents dimethylformamide, methyl glycol, diethylene glycol monomethyl ether are used to carry out the reaction and diethylene glycol dimethyl ether. The reaction is expediently carried out at temperatures carried out between 100 - 1500 C. As a catalyst in the hydrogenation in the second Firstly, Raney nickel or palladium on carbon are used.
Mit dem erfindungsgemäßen Verfahren wird eine einfache technische Herstellung der vorstehend näher beschriebenen Bis-(2,4-diaminophenoxy)-alkane ermöglicht.The method according to the invention is a simple technical one Production of the bis (2,4-diaminophenoxy) alkanes described in more detail above allows.
Die erfindungsgemäß hergestellten Bis-(2,4-diaminophenoxy)-alkane lassen sich mit Vorteil als solche oder in Gestalt ihrer Salze mit anorganischen oder organischen Säuren als Kupplerkomponenten in Oxidationshaarfarben zusammen mit den üblichen Entwicklersubstanzen einsetzen.The bis (2,4-diaminophenoxy) alkanes prepared according to the invention can advantageously be used as such or in the form of their salts with inorganic compounds or organic acids as coupler components in oxidation hair colors use with the usual developer substances.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn jedoch hierauf zu beschränken.The following examples are intended to illustrate the subject matter of the invention in greater detail explain without, however, restricting it to this.
Beispiele 1. Herstellung von 1,3-Bis-(2,4-diaminophenoxy)-propant etrahydrochlorid Stufe 1: Herstellung von 1,3-Bis-(2,4-dinitrophenoxy)-propan. Examples 1. Preparation of 1,3-bis (2,4-diaminophenoxy) propane Hydrochloride stage 1: Production of 1,3-bis (2,4-dinitrophenoxy) propane.
9,2 g 2,4-Dinitrophenol, angefeuchtet mit 0,6 g Wasser, wurden in 15 ml Diethylenglykoldimethylether suspendiert. Zu der Suspension wurden bei ca. 250 C 3,45 g Kaliumcarbonat gegeben. Die Suspension wurde hernach auf 1000 C erhitzt und es wurden 5 g 1, 3-Dibrompropan zugetropft. Anschließend wurde 4 Stunden lang auf 1250 C erhitzt. Nach dem Abkühlen wurde der erhaltene Niederschlag abgesaugt, mit Natronlauge und anschließend mit Wasser gewaschen. Nach dem Trocknen hatte das erhaltene 1,3-Bis-(2, 4-dinitrophenoxy)-0 propan einen Schmelzpunkt von 186 C. Die Ausbeute betrug 8,2 g, das sind 80 % der Theorie. 9.2 g of 2,4-dinitrophenol, moistened with 0.6 g of water, were in 15 ml of diethylene glycol dimethyl ether suspended. At approx. 250 C given 3.45 g of potassium carbonate. The suspension was then heated to 1000.degree and 5 g of 1,3-dibromopropane were added dropwise. This was followed by 4 hours heated to 1250 C. After cooling, the resulting precipitate was filtered off with suction, washed with sodium hydroxide solution and then with water. After drying that had obtained 1,3-bis- (2,4-dinitrophenoxy) -0 propane a melting point of 186 C. The The yield was 8.2 g, that is 80% of theory.
Stufe 2: Herstellung von 1,3-Bis-(2,4-diaminophenoxy)-propantetrahydrochlorid. Step 2: Preparation of 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride.
10 g 1,3-Bis-(2,4-dinitrophenoxy)-propan wurden in 50 ml Ethanol in Gegenwart von Raney-Nickel bei 25 atü und 250 C hydriert. 10 g of 1,3-bis (2,4-dinitrophenoxy) propane were in 50 ml of ethanol hydrogenated in the presence of Raney nickel at 25 atm and 250 C.
Nach beendeter Wasserstoffaufnahme wurde vom Katalysator abfiltriert. Die Lösung wurde mit conc. Salzsäure angesäuert und zur Trockne eingeengt. Das 1,3-Bis-(2,4-diaminophenoxy)-propantetrahydrochlorid wurde in Gestalt weißer Kristalle vom Schmelzpunkt 2150 C mit 95 %iger Ausbeute der Theorie erhalten. After the uptake of hydrogen had ended, the catalyst was filtered off. The solution was made with conc. Hydrochloric acid acidified and concentrated to dryness. 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride was in the form of white crystals with a melting point of 2150 C with a 95% yield get the theory.
2. Herstellung von 1,3-Bis-(2,4-diaminophenoxy)-propantetrahydrochlorid Stufe 1: Herstellung von 1,3-Bis-(2,4-dinitrophenoxy) propan.2. Preparation of 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride Step 1: Production of 1,3-bis- (2,4-dinitrophenoxy) propane.
Die Herstellung erfolgte völlig analog den Angaben in Beispiel 1, nur daß anstelle von Kaliumcarbonat zu der Suspension von 2,4-Dinitrophenol in Diethylenglykoldimethylether 2,8 g Kaliumhydroxid gegeben wurden. The production was carried out completely analogously to the information in Example 1, only that instead of potassium carbonate to the suspension of 2,4-dinitrophenol in diethylene glycol dimethyl ether 2.8 g of potassium hydroxide were added.
Die Ausbeute an 1,3-Bis-(2,4-dinitrophenoxy)-propan betrug 6,6 g, das sind 64 % der Theorie. The yield of 1,3-bis (2,4-dinitrophenoxy) propane was 6.6 g, that's 64% of theory.
Stufe 2: Entsprach völlig der Stufe 2 von Beispiel 1. Level 2: Corresponded entirely to level 2 of example 1.
3. Herstellung von 1,3-Bis-(2,4-diaminophenoxy)-propantetrahydrochlorid Stufe 1: Die Herstellung von 1,3-Bis-(2,4-dinitrophenoxy)-propan erfolgte analog den Angaben in Beispiel 1, wobei jedoch als Lösungsmittel 15 ml Methylglykol eingesetzt wurden.3. Preparation of 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride Stage 1: 1,3-bis- (2,4-dinitrophenoxy) propane was prepared analogously as in Example 1, but using 15 ml of methyl glycol as the solvent became.
Die Ausbeute an 1,3-Bis-(2,4-dinitrophenoxy)-propan betrug 6,6 g, das sind 64 % der Theorie. The yield of 1,3-bis (2,4-dinitrophenoxy) propane was 6.6 g, that's 64% of theory.
Stufe 2: Die Herstellung des 1,3-Bis-(2,4-diaminophenoxy)-propantetrahydrochlorids erfolgte analog der Stufe 2 von Beispiel 1. Step 2: The preparation of 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride took place analogously to step 2 of example 1.
4. Herstellung von 1 ,3-Bis-(2 ,4-diaminophenoxy) -propantetrahydrochlorid Stufe 1: Bei der analog der Stufe 1 von Beispiel 1 vorgenommenen Herstellung von 1,3-Bis- (2,4-dinitrophenoxy)-propan wurde bei diesem Beispiel als Lösungsmittel Diethylenglykolmonomethylether eingesetzt. Die Ausbeute an gewünschtem Zwischenprodukt betrug 7,5 g, das sind 74 % der Theorie.4. Preparation of 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride Stage 1: In the analogous to stage 1 of Example 1, the preparation of 1,3-bis- (2,4-dinitrophenoxy) propane was used in this example as Solvent diethylene glycol monomethyl ether used. The yield of the desired The intermediate product was 7.5 g, that is 74% of theory.
Stufe 2: Die weitere Verarbeitung zum Endprodukt erfolgte völlig analog zur Stufe 2 von Beispiel 1. Stage 2: The further processing to the end product took place completely analogous to step 2 of example 1.
5. Herstellung von 1,3-Bis-(2,4-diaminophenoxy)-propantetrahydrochlorid Stufe 1: Die Herstellung von 1,3-Bis-(2,4-dinitrophenoxy)-propan wurde entsprechend der Stufe 1 von Beispiel 1 mit 15 ml Dimethylformamid als Lösungsmittel durchgeführt.5. Preparation of 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride Step 1: The preparation of 1,3-bis- (2,4-dinitrophenoxy) propane was carried out accordingly carried out the stage 1 of Example 1 with 15 ml of dimethylformamide as a solvent.
Es wurden 5,1 g an gewünschtem Produkt erhalten, das sind 50 % der theoretischen Ausbeute. 5.1 g of the desired product were obtained, that is 50% of the theoretical yield.
Stufe 2: Die weitere Verarbeitung zum 1,3-Bis-(2,4-diaminophenoxy)-propantetrahydrochlorid erfolgte analog Stufe 2 von Beispiel 1. Step 2: Further processing to 1,3-bis- (2,4-diaminophenoxy) propane tetrahydrochloride took place analogously to step 2 of example 1.
Claims (5)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19792932460 DE2932460C2 (en) | 1979-08-10 | 1979-08-10 | Process for the preparation of 1,3-bis (2,4-diaminophenoxy) propane; |
NO793554A NO147302C (en) | 1978-12-02 | 1979-11-05 | HAIR COLOR ON BASIS OF OXYDATION COLORS |
FI793469A FI69752C (en) | 1978-12-02 | 1979-11-05 | HAORFAERGNINGSMEDEL |
DK467079A DK158441C (en) | 1978-12-02 | 1979-11-05 | HAIR PAINTING BASIS OF OXIDATION COLORS, BIS (2,4-DIAMINOPHENOXY) ALKANES FOR USE IN THE HAIR PAINTING AND PROCEDURE FOR THE PREPARATION OF BIS- (2,4-DIAMINOPHENOXYLE) |
US06/094,276 US4314809A (en) | 1978-12-02 | 1979-11-14 | Novel coupler components for oxidation hair dyes, the manufacture thereof, and hair colorants |
EP79104694A EP0011844B1 (en) | 1978-12-02 | 1979-11-26 | Coupling components for oxidizing hair dyes, their preparation and hair dyes containing them |
AT760079A AT368487B (en) | 1979-08-10 | 1979-11-30 | METHOD FOR PRODUCING BIS (2,4DIAMINOPHENOXY ALKANES |
AU53366/79A AU530720B2 (en) | 1978-12-02 | 1979-11-30 | Bis-(2,4-diamino-phenoxy) alkane coupler components |
BR7907807A BR7907807A (en) | 1978-12-02 | 1979-11-30 | BIS- (2,4-DIAMINOFENOXYL) -ALKANS, PROCESS FOR ITS PREPARATION, ITS APPLICATION, AND HAIR COLORING AGENTS |
AR279120A AR224256A1 (en) | 1978-12-02 | 1979-12-03 | NEW BIS- (2,4-DIAMINOFENOXI) ALKANS, PROCEDURE TO OBTAIN THEM AND HAIR DYES THAT CONTAIN THEM |
FI842781A FI76068C (en) | 1978-12-02 | 1984-07-11 | Process for the preparation of 1,3-bis (2,4-diaminophenoxy) propane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19792932460 DE2932460C2 (en) | 1979-08-10 | 1979-08-10 | Process for the preparation of 1,3-bis (2,4-diaminophenoxy) propane; |
Publications (2)
Publication Number | Publication Date |
---|---|
DE2932460A1 true DE2932460A1 (en) | 1981-02-19 |
DE2932460C2 DE2932460C2 (en) | 1982-10-14 |
Family
ID=6078135
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19792932460 Expired DE2932460C2 (en) | 1978-12-02 | 1979-08-10 | Process for the preparation of 1,3-bis (2,4-diaminophenoxy) propane; |
Country Status (2)
Country | Link |
---|---|
AT (1) | AT368487B (en) |
DE (1) | DE2932460C2 (en) |
-
1979
- 1979-08-10 DE DE19792932460 patent/DE2932460C2/en not_active Expired
- 1979-11-30 AT AT760079A patent/AT368487B/en not_active IP Right Cessation
Non-Patent Citations (3)
Title |
---|
Chem. Abstr. 57 (1962), 11074e * |
Compt.rend. 180 (1925), 1275 * |
J.pr. Chemie 27 (1883), 200 * |
Also Published As
Publication number | Publication date |
---|---|
ATA760079A (en) | 1982-02-15 |
DE2932460C2 (en) | 1982-10-14 |
AT368487B (en) | 1982-10-11 |
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