DD150059A1 - PROCESS FOR THE PRODUCTION OF HYDROXYARYLAZOLES - Google Patents

Abstract

Such compounds are important for the production of dyes and UV stabilizers. With the invention is to be achieved to synthesize hydroxyarylazoles in a one-step process from readily available starting materials. This is done in accordance with the invention by reacting hydroxyaryl aldehydes with arylamines and sulfur to form Type I hydroxyarylazoles. The invention can be used in the chemical industry.

Description

Int.Cl. GOTD'277 / GS C07D 263/62 C07D 233/22

The invention relates to a process for the preparation of hydroxyarylazoles I Such compounds have significance for the preparation of dyes and UV stabilizers.

Characteristic of the known technical solutions

It is known that hydroxyarylazoles can be cyclized from carboxylic acid and its derivatives with phenylenediamine, amiriophenols and aminothiophenols in the heat by means of condensing agents. [1.Kuroda, Y.Hashida, CA. 72, 122893a (1970); DWHein, RSLeavitt, J.Amer.Chem.Soc. .79, 427 (1957); JB Wright, Chem. Reviews 48, 397 C1951); A. Laddenburg, Ber.dtsch. ehem.Ges. 8, 577 (T857) and % T5.24 (1876); MAPhillips, J. Chem. Soc. (London) JH5, 474 (* 937); M.Heisse, diploma thesis IU Dresden (T97T); R. Schmidt, Dissertation CH Stuttgart (1962); R.Gompper et al., Ber.dtsch.ehem.Ges. 98_, t: 387 (19 & 5), Liebigs Ann.Chem. 684 , 37 (? 965); EHRodd, Chemistry of Carbon Compounds Vol.IV, Part A C1957)] It is also known that hydroxyarylazoles can be prepared by reduction of aromatic ITitroester or Mtroamide by means of tin-2-chloride and hydrochloric acid. [O.Kym, Ber.dtsch.ehem.Ges. _3g_, T427 (1899); ' J.Preston et al J. Heterocyclic Chem. _6, tT9 (196 "9)] It is also known that hydroxyarylazoles can be prepared by reacting aldehydes and their derivatives with the above amino compounds via Schiff bases (azomethines) under dehydrogenating conditions.

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[] cMorlando, JGWirth, DRHeath, J. Heterocyclic Chem. 7, T385 C197O); D.Jerchel, Liebigs Ann.Chem. 575, ΐ62 CT952); H.P.Iankelma, P.Sharnoff, J.Amer.Ghem.Soc. jT3, .2654 (1931); MT Bogert, J. Liner.Chein.Soc. 54, 379 (1932); 47, 3073 Ci925)] The known processes have the disadvantage that they are multi-step processes with low yield.

Aim of the invention

The aim of the invention is to synthesize hydroxyarylazoles from readily available starting products in a one-step process and in good yields.

Explanation of the essence of the invention

The object of the invention is. Eydroxyarylazole from readily available A _{US ARL} g g _{r S} p odukten to synthesize in one step and to complement the range of the previously known compounds by new agents. ·

According to the invention A _and fg _a -be is achieved in that hydroxyaryl al de de hy the%

with aryl amines of type II

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and sulfur to the Hvdroxyarylazolen type III

 R "

where R ₁ -, Rpbzw. R-, R _A and R, - and Rg are hydrogen, alkyl, aryl, alkoxy or in each case jointly a further fused substituted or unsubstituted -A-ryl- or heteroaryl ring and X is H or OH, EEL or SO ^ Ha and Y for 'the case that X is H or SCMTa an S, but otherwise a Q or HH fragment are reacted.

Embodiments.

The compounds prepared by the general procedure as examples are listed in Table 1.

General rule.

t Mpl hydroxyarylaldehyde, 1,5 'koi ^ vjlsanin and 2 moles of sulfur in 100-15OmI dimethylformamide are held at reflux for 10 hours just boiling. After cooling, the precipitated product is filtered off with suction, dried and recrystallized from suitable solvents (for example n-3-butanol, glacial acetic acid, siliceous ester, n-hexane, cyclohexane, toluene, uritromethane etc.).

wherein IL ·, R ₂ - or R, -R "sowie- R _n - and Rr is hydrogen, alkyl, aryl, alkoxy, or in each case together form a further fused substituted or unsubstituted aryl or heteroaryl ring and X is H or OH, ITH ₀ and SO-JTa and Y for the Pail, that X is H or SO ^ lTa an S- but otherwise represent a 0- or HH-I'ragment be implemented.

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ibelle · 1

Hydroxyaryl oil Type III

- (2'-hydroxyphenyl) -naphtho-?, T-d] -thiazole.

- (2'-hydroxyphenyl) -naphtho-?, T-d] -thiazole

  (2'-hydroxyphenyl) naphthols 2-d] thiazole

• (4'-hydroxyphenyl) -naphtho-!, T-d] -thiazole

• (2'-hydroxy-1'-naphthyl) phtho [1,2-d] thiazole

• (2'-hydroxy-T ♦ -naphthyl) -phtho- [2, T-d] thiazole

Methoxy-2- ^(2-hydroxy-r Lenyl) benzothiazole

Starting compound of formula type I Starting compound of formula type II Schm. ° C color '(Umlcrist.) Yield % of theory salicylaldehyde S-ITaphthylamin T66-T67 yellow (η-hexane) 67 salicylaldehyde ß-Naphthylamin- sulfonsaures Ifatrium. t65-T67 yellow. (Η-hexane) 58 salicylaldehyde • "c-naphthylamine T64-T65 light green (n-butanepl) 75 4-hydroxybenzaldehyde ß-Faphthylamin 238-24T green-yellow (glacial acetic acid) 54 2-hydroxynaphthaldehyde T "T-naphthylamine , T89-T91 brown (glacial acetic acid) 72 2-hydroxynaphthaldehyde T ~ beta-naphthylamine Τ86-Ϊ87 green (glacial acetic acid) 62 salicylaldehyde m-anisidine 1T9-120 beige (benzene) 60

Claims (1)

220 237 invention claim Process for the preparation of hydroxyarylazoles, characterized in that hydroxyarylaldehydes of the type I with arylamines of the type. II and sulfur too. the hydroxyarylazoles of type III