5960-55-4Relevant academic research and scientific papers
Formation of N-N and N-C Bond-Cleavage Products in Displacements with N,N-Disubstituted Hydrazines on 1-Halo- or 1,4-Dihaloanthracene-9,10-diones
Krapcho, A. Paul,Avery, Kenneth L.
, p. 5927 - 5929 (2007/10/02)
The displacements of 1-halo- and 1,4-dihaloanthracene-9,10-diones by N,N-disubstituted hydrazines have been studied.These reactions proceed via N-N bond cleavages of the hydrazine to yield products with the regiospecific incorporation of an N,N-disubstituted amino group.In addition, pyrazoles which arise from intermediates which undergo N-C bond cleavage are also formed.The ratio of the N-N to N-C cleavage products is dependent on the reaction solvent, temperature, structure of the hydrazine, and the nature of the leaving group being displaced from the anthracene-9,10-dione.For example, treatment of 1a with N,N-dimethylhydrazine in pyridine or dimethyl sulfoxide (DMSO) leads to 3a:2c ratios of 6 and 3, respectively.Compound 1e under comparable reaction conditions gives 3a:2c product ratios of 49 and 4, respectively.The dichloro dione 1c with N,N-dimethylhydrazine in pyridine or DMSO leads predominantly to 3b in 76percent and 72percent yields, respectively, with relatively little pyrazole 2d.The more reactive difluoro dione 1h on reaction with N,N-dimethylhydrazine in pyridine leads to N-N bond-cleavage products 3c (48percent) and 3d (40percent).Treatment of 1e with 1-piperidinamine in pyridine yields 3f.The results will be discussed.
REACTION OF 1-CHLORO- AND 1-NITROANTHRAQUINONES WITH 3-ALKYLAMINO- AND 3-DIALKYLAMINOPROPIONITRILES
Vostrova, V. N.,Plakidin, V. L.
, p. 939 - 942 (2007/10/02)
The reaction of 1-chloro- and 1-nitroanthraquinones with 3-alkylaminopropionitriles at 130-170 deg C leads to the formation of 1-alkylaminoanthraquinones; the reaction with 3-dialkylaminopropionitriles leads to 1-dialkylaminoanthraquinones, which undergo thermal cleavage under the reaction conditions (isoamyl alcohol, 130 deg C) with the formation of 1-alkylaminoanthraquinone.The nature of the substituted atom affects the reaction rate; the nitro group is substituted 54 times more quickly than the chlorine atom.The initial reaction rates in alcohols are 2-3 orders of magnitude higher than in benzene.
Anormalous Halogen to Dimethylamino Replacement with N,N-Dimethylformamide Catalyzed by Ethylenediamine or 2-Aminoethanol
Yamamoto, Hiroshi
, p. 2685 - 2686 (2007/10/02)
1- And 2-chloroanthraquinone and 2-amino-4-chloro-6-hydroxypyrimidine exclusively gave the dimethylamino derivatives upon heating in DMF at 90 deg C in the presence of ethylenediamine or ethanolamine.A possible reaction pathway for this unusual exchange reaction was discussed.
Reactions of 1,5-Dichloroanthrachinone with Nucleophiles
Ruediger, Edward H.,Kaldas, Magdy L.,Ghandi. Sham S.,Fedryna, Cristi,Gibson, Martin S.
, p. 1974 - 1978 (2007/10/02)
Reactions of 1,5-dichloroanthraquinone (1) with various nucleophiles were examined to evaluate possibilities for selective substitution. 1-Amino-5-chloroanthraquinone was obtained from 1 by reaction with (a) sodium azide in dimethyl sulfoxide and (b ammonia in the presence of potassium fluoride, but 1 with potassium in ammonia gave 3-chlorobenzoic acid.Conditions were found for preferential substitution in reactions of 1 with (c) 4-toluidine, (d) hexamethylphosphoric triamide, and (e) N-methylformamide.Reagent e is preferred for making 1-chloro-5-(methylamino)anthraquinone, though this compound predominates in mixtures produced when d is used.Potassium hydroxide in 2-ethoxyethanol converts 1 to the corresponding mono- and diethers of 1,5-dihydroxyanthraquinone, while sodium hydrosulfide and 1 give bis(5-chloroanthraquinonyl)sulfide.
