A Novel Ring Closure Reaction Between 1,4-Dihydroxyanthraquinone and Ethylenediamine Promoted by Copper Ions

Abstract

The reaction of 1,4-dihydroxyanthraquinone with ethylenediamine in the presence of Cu(I)Cl or Cu(II)Cl2 gave 6-hydroxy-1,2,3,4-tetrahydronaphtho- (2, 3-f) -quinoxaline- 7,12-dione in quantitative yield at ambient temperature. The reaction was promoted greatly by copper ions. The possible mechanism and the role of copper ions were discussed.

C−H Functionalization of 1,4-Naphthoquinone by Oxidative Coupling with Anilines in the Presence of a Catalytic Quantity of Copper(II) Acetate

“…Matsuoka and colleagues observed that a large excess of butylamine reacts with 5,8-dihydroxy-1,4-naphthoquinone in the presence of 2 mol equivalents of copper(II) salts to give a variety of products resulting from both nucleophilic substitution of the hydroxyl groups and oxidative coupling, whereas the analogous reaction with 1,4-dihydroxyanthraquinone selectively gave 2-butylamino-1,4-dihydroxyanthraquinone . A similar reaction with ethylenediamine gave a product resulting from oxidative addition and cyclization . Yoshida and co-workers found that N -alkylanilines regioselectively react at the 6-position with quinolin-5,8-dione in the presence of a molar equivalent of copper(II) acetate to give mixtures of products resulting from oxidative coupling to both the para position and the nitrogen of the aniline derivative .…”

“…40 A similar reaction with ethylenediamine gave a product resulting from oxidative addition and cyclization. 41 Yoshida and co-workers found that N-alkylanilines regioselectively react at the 6-position with quinolin-5,8-dione in the presence of a molar equivalent of copper(II) acetate to give mixtures of products resulting from oxidative coupling to both the para position and the nitrogen of the aniline derivative. and co-workers as part of their synthetic studies on the preparation of isoquinolindiones reported the oxidative coupling of amines with 5-isoquinolinol to give 8-dialkylamino-5,6-isoquinolinediones and the 7-isoquinolinol to give 3,5-(dialkylamino)-7,8-isoquinolinediones in the presence of 50 mol % copper(II) acetate.…”

Synthesis and Application of Crosslinking Blue Anthraquinone Polyamine Dye with High Fixation

“…Optimum reaction temperature was 50 °C, as lower temperature led to a slow reaction. High temperature led to the following reaction shown in Scheme 3 [13]:…”

Selective Hydrogenation of Quinizarins to Leuco-quinizarins and Their Direct Derivatization Using Flow-Batch-Separator Unified Reactors under Continuous-Flow Conditions

“…Leuco-quinizarin, characterized by its highly active diketone skeleton, serves as a versatile reactant capable of functioning as both an electrophile and a nucleophile. Its efficient conversion into a wide range of compounds has been recognized since Marschalk’s discovery in 1936. ,,,,,,,, Several methodologies for the synthesis of leuco-quinizarin from quinizarin, a readily available and cost-effective substrate, involve the use of stoichiometric amounts of inorganic reductants and bases or acids, such as sodium hydrosulfite (dithionite) bases, ,,,,,,,,,,,, Al(0) or Zn(0) acids, CuCl 2 acids, Fe 2+ acids, and SnCl 2 acids in most cases (Figure a). Although these synthetic methods have been widely used, large amounts of waste or toxic gas from stoichiometric reductants are generated; moreover, neutralization is required during the workup process.…”