DD274825A1 - PROCESS FOR THE PREPARATION OF ARYLENE-BISAZO NAPHTHYLAMINES - Google Patents

Abstract

The invention relates to a process for the preparation of arylene-bisazo-naphthylamines. Such compounds have significance as dyes for Anfaerben of fibers and plastics, as sensitizers for optoelectronic recording methods and as p H indicators in analytical chemistry. With the invention is to be achieved to synthesize the hitherto technically difficult to produce easily. This is done according to the invention in such a way that chlorine-substituted arylene-bisazo-naphthalenes are reacted with a primary amine at elevated temperature in a preferably dipolar aprotic solvent to give arylene-bisazo-naphthylamines III. Formula III

Description

RNN-O-N-N-Ar-N-N-O-NHR

\ J W //

wherein Ar and R have the same meaning as in formula I and II are reacted.

AusfQhrungsbelsplele

The invention will be explained in more detail below with reference to the compounds listed in Table 1 and synthesized according to the following illustration variant.

0.1 Niol the chlorine-substituted Bisarylazoverbindi "-. _A. Jn are dissolved in 500ml DMF and unoccupied with 200ml of the primary amine is then heated on a water bath and the reaction progress TLC ^ as long vorfolgt until no more starting material is detectable At this time, The reaction mixture was allowed to cool, poured into 50 ml of glacial acetic acid and filtered with suction from the precipitate, followed by recrystallization from glacial acetic acid.

Tabeile J Fp (X) (ref Fp) Yield (% of theory) R: (Ar: 1,4-phenylon) 230 51.0 RC ₄ H ₉ - 241- ^ 3 53 RC ₆ Hu 23-4-31 " 53 nC ₈ H, 7 212 (212) 50 C ₄ H ₆ - 219-21 50.5 CßHior " 216 49.0 221 49 4-CHr-C ₄ H ₄ - 234 48.5 4-CH ₃ OC ₆ H ₄ - (Ar: 4,4'-biphenylene) 26 & -Ü9 54.5 RC ₄ -H ₉ - 276 57 n-Cj-Hu 272-74 58.5 nC ₆ H "- 320 (321) 50 C ₆ H ₆ - 283-85 43.5 C ₆ HiO- 291-93 49.5 C ₆ Hg-CH2 301 48 4-CH ₃ -C ₆ H ₄ - 272-76 49.5 4-CH ₃ OC ₄ H ₄ -

Claims (1)

Process for the preparation of arylene-bisazo-naphthylamines, characterized in that chlorine-substituted arylenebisazonaphthalenes of the formula I ₁ which are relatively easy to prepare from industrially readily available arylenebisazo-naphthols by reaction with POCl 3 / DMF, where Ar-phenylene, biphenylene , Naphthylen, Oxybiphenylen and other bifunctional arylene compounds, with a primary amine of the general formula II, wherein R is any aliphatic or aromatic radical which in the former case of simple unbranched or branched carbon chains of one to eighteen atoms and in the latter case of simple unsubstituted or optionally substituted phenyl radicals, is, at temperatures around 1000 ⁰ C, using a dipolar aprotic solvent such as DMR, DMSO, HMPT or acetonitrile compounds of the general formula type III, wherein Ar and R have the same meaning as in de n formulas I and II have been implemented. Field of application of the invention The invention relates to a process for the preparation of arylene-blsazc-napUhylaminen. Such compounds are important as dyes for dyeing fibers and plastics, as sensitizers for electro-optical recording methods and as pH indicators in analytical chemistry. Characteristic of the known technical solution It is known that arylenebisazo-naphthylamines can be prepared by tetrazotization of primary aromatic diamines with nitrous acid and subsequent coupling of the resulting aiyltetrazonium salts with N-alkyl- or N-aryl-substituted 1-naphthylamines (reference MAJSCHOUTISSEN, J. Amer Soc., 1933, 4541). However, said method has the disadvantage that the necessary N-substituted 1-naphthylamino technically not always easy and in the required purity can be displayed and beyond a high sensitivity to oxidation and a z. T. have significant adverse health effect, which greatly limits their use in the art or practically excludes. Object of the invention The aim of the invention is to make the technically hitherto not easily produced and usable as dyes, spectral Sencibilisatoren and as pH indicators arylene-bisazo-naphthylamine in a simple manner zugänglicn. Explanation of the essence of the invention The object of the invention is to make the aryl-bisazo-naphthyl-mines, which have not hitherto been problematic, accessible in a simple manner from readily available and easily handled starting materials in high purity and good yields. According to the invention, this object is achieved by the chlorine-substituted arylene-bisazo-naphthalenes of the formula I, which are readily and conveniently prepared from industrially readily available starting materials according to DD 155986, Ar being phenylene, biphenylene, naphthylene, oxibiphenylene and other bifunctional arylene compounds, CL-O-N = N- with a primary amine of general formula II R-NH ₂ II wherein R represents any aliphatic or aromatic rust, which in the former case may consist of simple unbranched or branched carbon chains of one to eighteen atoms and in the latter case of simple unsubstituted or optionally substituted phenyl radicals, in a preferably dipolar aprotic solvent such as DMF, DMSO , HMPT or CH ₃ N at temperatures around 100 ° C to compounds of the general formula III