DE2660747C2 - Aminophenol ethers and their preparation - Google Patents

Aminophenol ethers and their preparation

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Publication number
DE2660747C2
DE2660747C2 DE19762660747 DE2660747A DE2660747C2 DE 2660747 C2 DE2660747 C2 DE 2660747C2 DE 19762660747 DE19762660747 DE 19762660747 DE 2660747 A DE2660747 A DE 2660747A DE 2660747 C2 DE2660747 C2 DE 2660747C2
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DE
Germany
Prior art keywords
ethers
preparation
formula
aminophenol
aminophenol ethers
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
Application number
DE19762660747
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German (de)
Inventor
Hubertus Dr. 5060 Leverkusen Psaar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DE19762660747 priority Critical patent/DE2660747C2/en
Priority claimed from DE2631166A external-priority patent/DE2631166C2/en
Application granted granted Critical
Publication of DE2660747C2 publication Critical patent/DE2660747C2/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B19/00Oxazine dyes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

wormworm

Ri Wasserstoff, Q-GrAlkyl, C2- oder C3-Alkenyl, jff-Cyanethyl, /7-Hydroxyethyl, yJ-Hydroxvpropyl, ^-Chiorethyl, /J-Q-GrAlkoxyethyl, ^-Ci-Ci-Alkoxypropyl oder /7-Carbonamidoethyl,Ri hydrogen, Q-GrAlkyl, C 2 - or C 3 -alkenyl, jff-cyanoethyl, / 7-hydroxyethyl, yJ-Hydroxvpropyl, ^ -Chiorethyl, / JQ-Gralkoxyethyl, ^ -Ci-Ci-Alkoxypropyl or / 7-Carbonamidoethyl ,

R2 C2-C4-AIlCyI, C2- oder C3-AlkenyL, /F-Cyanethyl, /?-Hydroxyethyl, ^-Hydroxypropyl, /J-Chloretbyl,R 2 C 2 -C 4 -AIlCyI, C 2 - or C 3 -alkenyL, / F-cyanoethyl, /? - hydroxyethyl, ^ -hydroxypropyl, / J-chlororetbyl,

/J-Ci-Q-Alkoxyethyl, yS-Ci-Ci-Alkoxypropyl oder yS-Carbonamidoethyl, 20 R3 Wasserstoff-Ci-C4-AIkVl oder Cj-C4-AIkOXy und η 1 oder 2 bedeuten./ J-Ci-Q-alkoxyethyl, yS-Ci-Ci-alkoxypropyl or yS-carbonamidoethyl, 20 R 3 hydrogen-Ci-C 4 -AIkVl or Cj-C 4 -AIkOXy and η 1 or 2 mean.

2. Aminophenolether gemäß Anspruch 1 mit der Formel2. aminophenol ethers according to claim 1 having the formula

CH ί J CH3 CH ί J CH 3

0-CH2-CH-OH0-CH 2 -CH-OH

/ 30 C2H5 / 30 C 2 H 5

3. Verfahren zur Herstellung von Aminophenolethern des Anspruchs 1, dadurch gekennzeichnet, daß man in an sich bekannter Weise der Aminophenole der Formel3. Process for the preparation of aminophenol ethers of claim 1, characterized in that one in a conventional manner of the aminophenols of the formula

OHOH

worinwherein

Ri-Rj die in Anspruch 1 angegebene Bedeutung haben,Ri-Rj have the meaning given in claim 1,

mit Propylenoxid umsetzt.Reacts with propylene oxide.

Gegenstand der Erfindung sind Aminophenolether der FormelThe invention relates to aminophenol ethers of the formula

I (D II (D I

(Ο —CH2-CH)n-OH(Ο -CH 2 -CH) n -OH

65 Ri Wasserstoff, Ci-C4-Alkyl, C2- oder C3-Alkenyl, yS-Cyanethyl, /7-Hydroxyethyl, /Ϊ-Hydroxypropyl, /?-Chlorethyl, /J-Ci-Ci-Alkoxyethyl, ^-Ci-Q-Alkoxypropyl oder /7-Carbonamidoethyl,65 Ri hydrogen, Ci-C 4 -alkyl, C 2 - or C 3 -alkenyl, yS-cyanoethyl, / 7-hydroxyethyl, / Ϊ-hydroxypropyl, /? - chloroethyl, / J-Ci-Ci-alkoxyethyl, ^ - Ci-Q-alkoxypropyl or / 7-carbonamidoethyl,

R2 C2-GrAIkVl, C2- oder C3-Alkenyl, /?-Cyanethyl, /J-Hydroxyethyl, /7-Hydroxypropyl, /3-Chlorethyl, )S-Ci- Q-Alkoxyethyl, )S-Ci^Ct-Alkoxypropyl oder yff-Carbonamidoethyl,R 2 C 2 -GrAIkVl, C 2 - or C 3 -alkenyl, /? - cyanoethyl, / J-hydroxyethyl, / 7-hydroxypropyl, / 3-chloroethyl,) S-Ci- Q-alkoxyethyl,) S-Ci ^ Ct-alkoxypropyl or yff-carbonamidoethyl,

R3 Wasserstoff, Ci-GrAlkyl oder Ci-C4-AIkOXy und
π 1 oder 2 bedeuten,
R 3 is hydrogen, Ci-GrAlkyl or Ci-C 4 -AIkOXy and
π mean 1 or 2,

und ihre Herstellung.
Von den Ethern der Formel I sind die Ether a — d der Formel
and their manufacture.
Of the ethers of the formula I, the ethers a - d of the formula

CH3 Ο —CH2-CH-OHCH 3 Ο -CH 2 -CH-OH

(Π)(Π)

RiRi

R2 R 2

R3 R 3

a b ca b c

C2H5 HC 2 H 5 H

CH3 HCH 3 H

C2H5 C 2 H 5 HH C2K5 C 2 K 5 C2H4CNC 2 H 4 CN HH C2H4CNC 2 H 4 CN OCH3 OCH 3

bevorzugt und die Verbindung Ka hervorzuheben.preferred and the compound Ka to be emphasized.

Aminophenolether der Formel (I) lassen sich nach der von D. R. Boyd und E. R. Marie in Journal of the Chemical Society 105, (1914), Seiten 2117-2139, beschriebenen Methode durch Umsetzung von Aminophenolen der FormelAminophenol ethers of the formula (I) can be prepared according to the method described by D. R. Boyd and E. R. Marie in Journal of the Chemical Society 105, (1914), pages 2117-2139, described method by reacting aminophenols the formula

OHOH

1010

1515th

2020th

2525th

3030th

Ri, R2 und R3 die vorstehend genannte Bedeutung haben, mit Propylenoxid herstellen.Ri, R 2 and R 3 have the meaning given above, produce with propylene oxide.

Aus der genannten Veröffentlichung ist die - hier nicht beanspruchte - Verbindung der Formel (I), in der Ri und R2 für Methyl, R3 für Wasserstoff und η für 1 stehen, bekannt.From the publication mentioned, the compound of the formula (I) - not claimed here - in which Ri and R 2 are methyl, R 3 is hydrogen and η is 1, is known.

Die Umsetzung der Aminophenole (III) mit Propylenoxid erfolgt in Anwesenheit von geringen Mengen Alkali bei Temperaturen von 80 bis 120° C.The aminophenols (III) are reacted with propylene oxide in the presence of small amounts Alkali at temperatures from 80 to 120 ° C.

Die Aminophenolether der Formel (I) lassen sich durch Nitrosierung und anschließende Umsetzung mit Phenolen zu bekannten basischen Oxazinfarbstoffen umsetzen.The aminophenol ethers of the formula (I) can be converted into by nitrosation and subsequent reaction Convert phenols to known basic oxazine dyes.

Das aus der Propoxylierung erhaltene Reaktionsgemisch kann entweder direkt oder nach der Reinigung zur Farbstoffherstellung weiterverarbeitet werden.The reaction mixture obtained from the propoxylation can either be used directly or after purification Dye production can be further processed.

Die Aminophenolether (I) eignen sich insbesondere zur Herstellung der Oxazinfarbstoffe nach einem mehrstufigen Eintopfverühren, bei dem weder die Phenolether (I) noch ihre Nitrosoverbindungen, die im wäßrigen Reaktionsroedium in gelöster Form vorliegen, isoliert weraen. Auf diese Weise werden die Farbstoffe auf technisch gut durchführbare Weise und - im Vergleich zu bekannten Verfahren - in gleicher oder sogar verbesserter Reinheit und Ausbeute erhalten.The aminophenol ethers (I) are particularly suitable for preparing the oxazine dyes in a multistage manner One-pot mixing, in which neither the phenol ethers (I) nor their nitroso compounds, which are in the aqueous Reaction media are present in dissolved form, are isolated. This way the dyes will be on Technically well feasible manner and - compared to known methods - in the same or even better way Maintain purity and yield.

Aus der DE-OS 15 69 604 und der DE-OS 24 58 347 sind Verfahren zur Herstellung basischer Oxazinfarbstoffe bekannt, bei denen die durch Nitrosierung von m-Hydroxy- oder m-Alkoxyanilinen in wäßrig-alkoholischem Medium erhaltenen Suspensionen von p-Nitroso-m-hydroxy- oder p-Nitroso-m-alkoxy-anilinen ohne Isolierung mit m-AminophenoIen, m-Aminophenolethern oder m-Phenylendiaminen kondensiert werden. Laut DE-OS 2458 347, Anspruch 1, können zwar außer den Suspensionen auch Lösungen zur Kondensation verwendet werden, in Beschreibung und Beispielen wird aber kein Hinweis gegeben, wie diese Lösungen !herstellbar sind.From DE-OS 15 69 604 and DE-OS 24 58 347 are processes for the preparation of basic oxazine dyes known in which the nitrosation of m-hydroxy or m-alkoxyanilines in aqueous-alcoholic Medium obtained suspensions of p-nitroso-m-hydroxy- or p-nitroso-m-alkoxy-anilines without isolation be condensed with m-aminophenols, m-aminophenol ethers or m-phenylenediamines. According to DE-OS 2458 347, claim 1, can, in addition to the suspensions, also solutions for condensation can be used, but no indication is given in the description and examples of how these solutions are used ! can be produced.

Aus der DE-OS 20 64 735 ist ein Herstellungsverfahren für basische Oxazinfarbstoffe durch Cyclisierung von isolierten 2-Amino-5-nitroso-hydrochinon-dialkylethern mit 3-Aminophenolen bekannt. Laut Beschreiibung kann der Alkylrest der Ethergruppe, die bei der Cyclisierung abgespalten wird, durch Reste wie Hydroxyl substituiert sein. Aus diesem Hinweis konnte jedoch nicht die Lehre entnommen werden, daß die erfmdungsgemäßen Ether (I) in Nitrosoverbindungen überfuhrbar sind, die aufgrund ihrer guten Wasserlöslichkeit ohne Zwischenisolierung in einem Eintopfverfahren mit Phenolen zu Farbstoffen cyclisiert werden können.From DE-OS 20 64 735 a production process for basic oxazine dyes by cyclization of isolated 2-amino-5-nitroso-hydroquinone dialkyl ethers with 3-aminophenols are known. According to the description the alkyl radical of the ether group which is split off in the cyclization can be substituted by radicals such as hydroxyl be. From this reference, however, the teaching could not be inferred that the inventive Ether (I) can be converted into nitroso compounds which, because of their good solubility in water, do not require intermediate isolation can be cyclized to dyes in a one-pot process with phenols.

4040

4545

5050

5555

6060

6565

Beispielexample

165 Gew.-Teile 3-Diethylaminophenol und 2 Gew.-Teile Triethanolamin werden unter Stickstoff auf 90° C erwärmt Dann werden unter Rühren in 1 Stunde 65 Gew.-Teile Propylenoxid eingeleitet. Es wird 5 Stunden bei 140° C nachgerührt, auf Raumtemperatur abgekühlt und Propylenoxid mit Stickstoff abgeblasen. Man erhält 231 Gew.-Teile eines Reaktionsproduktes, das 95% des 3-Diethylamino-phenyl-^-hydroxypropylethers enthält Die Ausbeute beträgt 99% der Theorie. Der Ether kann ohne weitere Reinigung zur Synthese von kationischen Oxazinfarbsioffen eingesetzt werden.165 parts by weight of 3-diethylaminophenol and 2 parts by weight of triethanolamine are brought to 90 ° C. under nitrogen Then, with stirring, 65 parts by weight of propylene oxide are passed in over 1 hour. It will be 5 hours at 140 ° C, cooled to room temperature and blown propylene oxide with nitrogen. You get 231 parts by weight of a reaction product which contains 95% of 3-diethylaminophenyl - ^ - hydroxypropyl ether The yield is 99% of theory. The ether can be used without further purification for the synthesis of cationic Oxazine dyes are used.

Die Reinigung und Gewinnung des Ethers erfolgt durch Destillation. Er hat einen Siedepunkt von 188 bis 190° C/20 mbar. Die Identifizierung erfolgte durch IR- und NMR-Spektrum.The ether is purified and recovered by distillation. It has a boiling point of 188 to 190 ° C / 20 mbar. Identification was carried out by means of the IR and NMR spectrum.

Claims (1)

Patentansprüche:Patent claims: L Amrnophenolether der Formel R3 L Amminophenol ethers of the formula R 3 CH3 CH 3 I (DI (D (O — CH2- CH)„— OH(O - CH 2 - CH) "- OH
DE19762660747 1976-07-10 1976-07-10 Aminophenol ethers and their preparation Expired DE2660747C2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19762660747 DE2660747C2 (en) 1976-07-10 1976-07-10 Aminophenol ethers and their preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19762660747 DE2660747C2 (en) 1976-07-10 1976-07-10 Aminophenol ethers and their preparation
DE2631166A DE2631166C2 (en) 1976-07-10 1976-07-10 Process for the preparation of oxazine dyes

Publications (1)

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DE2660747C2 true DE2660747C2 (en) 1985-07-11

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Application Number Title Priority Date Filing Date
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR799142A (en) * 1935-03-05 1936-06-06 Cie Nat Matieres Colorantes Process for the manufacture of dyes for cellulose esters, and resulting products
DE2064735A1 (en) * 1970-12-31 1972-08-03 Farbwerke Hoechst AG, vormals Meister Lucius & Brüning, 6000 Frankfurt Basic oxazine dyes and process for their preparation
DE2458347A1 (en) * 1974-12-10 1976-06-16 Hoechst Ag PROCESS FOR THE PREPARATION OF BASIC OXAZINE DYES

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR799142A (en) * 1935-03-05 1936-06-06 Cie Nat Matieres Colorantes Process for the manufacture of dyes for cellulose esters, and resulting products
DE2064735A1 (en) * 1970-12-31 1972-08-03 Farbwerke Hoechst AG, vormals Meister Lucius & Brüning, 6000 Frankfurt Basic oxazine dyes and process for their preparation
DE2458347A1 (en) * 1974-12-10 1976-06-16 Hoechst Ag PROCESS FOR THE PREPARATION OF BASIC OXAZINE DYES

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ein Versuchsbericht liegt zur Akteneinsicht vor
J.Amer.Chem.Soc., 60, 1938, 1582-4 *

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