60316-43-0Relevant academic research and scientific papers
STRUCTURE OF THE BORATE COMPLEXES OF α-AMINO AND α-HYDROXY-9,10-ANTHRAQUINONES AND THEIR REACTION WITH AMINES
Gorelik, M. V.,Shapet'ko, N. N.,Arinich, L. V.,Tsurkan, A. I.,Kukushkina, M. L.
, p. 547 - 556 (2007/10/02)
It was shown by 13C NMR that a redistribution of the bonds with partial localization of the 1,5- and 1,10-anthraquinonoid structures occurs during the transition from 1,5-diamino(dihydroxy)- and 1-amino(hydroxy)-9,10-anthraquinones respectively to their borate complexes.For this reason the boroacetates and fluoroborates of 1,5-dihydroxyanthraquinonones, 1-aminoanthraquinones, their N-alkyl and N-aryl derivatives, and 1,5-dihydroxyanthraquinone are capable of entering into amination under the influence of aromatic amines with substitution of the hydrogen atom at position 4 under mild conditions with the participation of atmospheric oxygen as oxidizing agent
Process for the manufacture of N-alkylamino- and N,N-dialkylaminoanthraquinones
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, (2008/06/13)
A process for the manufacture of N-alkylamino- and N,N-dialkylaminoanthraquinone from the corresponding nitroanthraquinones, which comprises reacting substituted or unsubstituted nitroanthraquinones or dinitroanthraquinones with at least twice the molar amount, referred to the nitro groups to be reacted, of an alkyl acid amide, at temperatures between 100° C and the boiling point of the alkyl acid amide. The present invention provides a process for the manufacture of N-alkylamino- and N,N-dialkylaminoanthraquinones from the corresponding nitroanthraquinones, which process comprises reacting substituted or unsubstitued nitroanthraquinones or dinitroanthraquinones with at least twice the molar amount, referred to the nitro groups to be reacted, of an alkyl acid amide which is simultaneously reactant and reaction medium, at temperatures between 100° C and the boiling point of the alkyl acid amide. The reaction takes place according to the general reaction equation STR1 wherein R and R', which are the same or different, represent alkyl, aralkyl, cycloalkyl or hydroxyalkyl radicals of 1 to 8 carbon atoms, n is 0 or 1, X represents a functional substituent, for example the carboxyl, sulpho, hydroxy, amino or halogen group, which can be attached direct or through a bridge member to the anthraquinone nucleus. The reaction can be carried out with mononitroanthraquinones and/or dinitroanthraquinones. The aminoanthraquinones obtained by the process of this invention are known and are useful dyes or dyestuff intermediates. The aminolysis of nitroanthraquinones is described in German Pat. Nos. 136.777, 136.778 and 144.634. However, polar solvents, such as water, alcohols or pyridine, are used as reaction media therein. The use of polar solvents as reaction media results in only very poor yields and lengthy reaction times are required. For example, the reaction of 1-nitroanthraquinone with a 300% excess of isopropylamine at 75° C after 100 hours gives a yield of only 70% of 1-isopropylaminoanthraquinone. Swiss Pat. application No. 12793/74 describes the aminolysis by reacting nitroanthraquinones with organic amines using dipolar aprotic solvents which contain --SO2 or --SO groups as reaction media. This process is satisfactory up to the recovery of the solvents used as reaction medium, which may have to be separated by distillation from the amines used as reactants. By comparison, N-alkylamino- and N,N-dialkylamino-anthraquinones are obtained surprisingly in very high and often even quantitative yields by the process of this invention. The products are obtained in a high degree of purity, so that mostly they do not need to be purified any more. The reaction conditions are simple and the reaction course is easily kept under control. No problems regarding corrosion or of a technical nature arise in respect of the apparatus used and the recovery of the excess acid amide used as reaction medium presents no difficulties. The reaction course is uniform and virtually no residues occur, so that the process of this invention also marks a considerable advance especially from the ecological standpoint. The excess acid amide can be almost completely recovered after the reaction by simple distillation or by filtering it off from the product, and reused for a fresh batch. Examples of aminoanthraquinones which can be obtained by the process of this invention are: 1-isopropylaminoanthraquinone, 1-isobutylamino-2-methylanthraquinone, 1-methylaminoanthraquinone, 1-diethylaminoanthraquinone, 1-cyclohexylaminoanthraquinone, the sodium salt of 1-isopropylaminoanthraquinone-6/7-sulphonic acid, 1-isobutylaminoanthraquinone, 1-diisopropyl-, 1-diisobutyl- and 1-dicyclohexylaminoanthraquinone, 1-isopropylamino-2-methylanthraquinone 1-cyclohexylamino-2-methylanthraquinone, 1,5-bis-methylaminoanthraquinone and 1-dimethylaminoanthraquinone. The aminolysis is carried out in conventional reaction vessels or autoclaves. A suitable apparatus is the rotary evaporator or, for batches produced on an industrial scale, the paddle drier (Venulett). The reaction temperature will be at least 100° C. The preferred reaction temperature is between 160° and 200° C. The aminolysis can be carried out both under pressure and without pressure. It is preferred to operate without pressure. The reaction time is from 0.5 to 15 hours, preferably 1 to 5 hours. The weight ratio of the acid amide as reactant and reaction medium to the nitroanthraquinone is advantageously between 4:1 to 10:1. Suitable acid amides are those of the formulae HCONHR, RCONHR, HCONRR', RCONNRR' or those of the formulae PO(--NRR')3, SO2 (--NRR')2 or SO(--NRR')2, wherein R and R', which are the same or different, represent alkyl, aralkyl, cycloalkyl or hydroxyalkyl radicals of 1 to 8 carbon atoms. An alkyl group represented by each of R and R' can be the same or different, straight-chain or branched, and is in particular a low molecular alkyl group of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert.butyl, or a long-chain alkyl group, such as hexyl or octyl. A cycloalkyl group represented by each of R and R' is in particular the cyclohexyl group and an aralkyl group represented by R and R' is above all the benzyl or phenethyl group. Preferably each of R and R' represents a lower alkyl group. Examples of acid amides which can be used according to the invention are: N-methyl formamide, N-methyl acetamide, N,N-dimethyl formamide, N-ethyl formamide and hexamethylphosphoric triamide or tetramethyl thionyl diamide. The reaction is carried out, for example, in such a way that the reactants, nitroanthraquinone and acid amide, are charged into a reaction vessel and stirred for several hours at temperatures between 100° and 200° C. When the reaction is complete, the excess acid amide is distilled off and can be reused. In many cases the product crystallises out after the reaction mixture has cooled, so that it is separated by filtration, and the mother liquor (i.e., excess acid amide with a small amount of dissolved product) can be reused for further reactions. It will be readily understood that the products can also be isolated by diluting the reaction mixture with water or alcohols and subsequent filtration. The following Examples illustrate the process of the present invention without implying any restriction to what is described therein. The parts are by weight.
