Reactions of 9-chloro-1,10-anthraquinone 1-dichlorophosphorylimine with N- and C-nucleophiles

Abstract

9-Chloro-l,10-anthraquinone l-dichlorophosphorylimine formed in the reaction of I-amino-9,10-anthraquinone with PCI 5 followed by dehydrochlorination reacts with primary amines with substitution of chlorine atoms. In the case of aliphatie amines, the reaction occurs further concurrently in two directions: the addition of the amine molecule with the formation of 9,9-di(alkylamino) derivatives of the anthrone and the substitution of hydrogen atom at position 4 with the formation of 4,9-di(alkylamino) derivatives of 1,10-anthraquinone 1 Amine. In the case of aromatic amines, l-amino-9,10-anthraquinone 9-arylimines are the end products. Reactions with the anions of CH-acids containing an alkoxycarbonyl or cyano group occur with substitution in position 9 followed by intramolecular cyclization with the formation of 2-alkoxy-or 2-amino-7H-dibenzo[f,/j]isoquinolin-7-one derivatives, respectively.

Syntheses of 7H-pyrido-and 7H-pyrano[2,3,4-kl]acridin-2(3H)-ones from 9-chloroacridines

“…In the case of ethyl malonate, the cyclization yielded a mixture of 2 ethoxy 1 ethoxycarbonyl 7 methyl 7H pyrido [2,3,4 kl]acridine (2b) and 1 ethoxycarbonyl 7 methyl 7H pyrido[2,3,4 kl]acridin 2(3H ) one (3b) in approximately the same ratio as for products 2a and 3a.…”

“…Earlier, 1 we have described the synthesis of pyrido[kl]acridines by cyclization of 1 acylamino acridones. Treatment of aminoacridone 1 with PCl 5 in benzene and then with a CH acid in the presence of a base directly gave pyri do [2,3,4 kl]acridine derivatives. A literature example of [kl]annula tion of a heterocycle with acridine is a transformation of 9 ethynyl 1,4 dimethoxyacridine into 6 methoxy 3H pyrido [2,3,4 kl]acridine in the presence of sodium di formylamide, which is regarded as electrocyclic ring clo sure in the enamide anion.…”

“…Here we present another route to these hetero cycles via replacement of the halogen atom in 1 substi tuted 9 chloroacridine by a C nucleophile followed by an attack of its electrophilic α functional group on the sub stituent in position 1. With ethyl cyanoacetate as a CH acid, 1 cyano 2 ethoxy 7 methyl 7H pyri do [2,3,4 kl]acridine (2a) and 1 cyano 7 methyl 7H pyrido [2,3,4 kl]acridin 2(3H ) one (3a) were obtained in the ratio ~3 : 1 (Scheme 1). 2 9 Chloroacridine containing the amino group in posi tion 1 was generated by a reaction of 1 amino 10 methylacridone (1) with PCl 5 (by analogy with a known 3 reaction of 1 aminoanthraquinone with PCl 5 ).…”