Reactions of 9-Chloro-1,10-anthraquinone-1-dichlorophosphorylimine with N-and C-Nucleophiles.-9-Chloro-1,10-anthraquinone-1-dichlorophosphorylimine, formed in situ by reaction of 1-amino-9,10anthraquinone (I) with PCl 5 and subsequent dehydrohalogenation, undergoes substitution of the chlorine atom on reaction with primary amines. With aromatic amines such as aniline, 1-amino-9,10-anthraquinone-9-arylimines [cf. (X)] are formed. Two alternative pathways are observed in reactions with aliphatic amines such as cyclohexylamine: addition of amine to the position 9 to afford the 9,9-di(alkylamino)-1-aminoanthrone [cf. (XII)] or substitution of hydrogen and chlorine at positions 4 and 9, respectively. The reaction with CH-acids such as diethyl malonate in the presence of base leads to the 2-alkoxy-(III) and (VII) or 2-aminodibenzo[f,ij]isoquinolin-7-one derivatives (IV) due to ring closure involving the functional group of the CH-acid. -(GORELIK, M. V.; TITOVA, S. P.; GLADISHEVA, T. H.; Izv.
Synthesis of 9-Chloro-1,10-anthraquinone and Its Reactions with Amines.-Reaction of 1-hydroxy-9,10-anthraquinone (I) with PCl 5 affords 1-dichlorophosphoryloxy-9,9-dichloroanthrone (II) which on reaction with cyclohexylamine in benzene undergoes amination of the phosphoryloxy group to give compound (IV). This compound (IV) is further aminated in refluxing toluene affording 9-imino-1-diaminophosphoryloxyanthrone (VI). The reaction with aniline does not stop at the first amination step and provides the corresponding 9-imino analogue (IX) immediately. The amination of 9,9-dichloro-1-dichlorophosphoryloxyanthrone (II) in DMF starts at the free position 4 to afford 4-amino-9-chloro-1,10-anthraquinone (XI), while the second amination step proceeding at position 9 is realized in refluxing benzene. The amination of compound (II) in DMF is proposed to go via 9-chloro-1,10anthraquinone, which can not be isolated in pure form. -(GORELIK, M. V.; TITOVA, S. P.; GLADISHEVA, T. H.; Izv.
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