- Synthesis and solid state structure of fluorous probe molecules for fluorous separation applications
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A series of colored hydrocarbon and fluorocarbon tagged 1-fluoro-4-alkylamino-anthraquinones and 1,4-bis-alkylamino-anthraquinone probe molecules were synthesized from a (fluorinated) alkyl amine and 1,4-difluoroanthraquinone to aid in the development of fluorous separation applications. The anthraquinones displayed stacking of the anthraquinone tricycle and interdigitation of the (fluorinated) alkyl chains in the solid state. Furthermore, intramolecular N-H?O hydrogen bonds forced the hydrocarbon and fluorocarbon tags into a conformation pointing away from the anthraquinone tricycle, with the angle of the tricycle plane normal and the main (fluorinated) alkyl vector ranging from 1° to 39°. Separation of the probe molecules on fluorous silica gel showed that the degree of fluorination of the probe molecules plays only a minor role with most eluents (e.g., hexane/ethyl acetate and methyl nonafluorobutyl ethers/ethyl acetate). However, toluene as eluent caused a pronounced separation by degree of fluorination for fluorocarbon, but not hydrocarbon tagged probe molecules on both silica gel and fluorous silica gel. These studies suggest that hydrocarbon and fluorocarbon tagged anthraquinones are useful probe molecules for the development of laboratory scale fluorous separation applications.
- Lehmler,Telu,Vyas,Shaikh,Rankin,Knutson,Parkin
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- Facile synthesis of 1-butylamino- and 1,4-bis(butylamino)-2-alkyl-9,10-anthraquinone dyes for improved supercritical carbon dioxide dyeing
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Supercritical carbon dioxide (scCO2) has recently been conquering both material sciences and process engineering owing to its intriguing properties like high diffusivity and tuneable (de)solubilizing performance. However, except for impregnation with biocidal preservatives, utilization of scCO2 for modification of wood including dyeing has been hitherto less explored. Therefore, we recently proposed a green wood dyeing approach that relies on the excellent carrier medium properties of CO2 for non-polar disperse dyes in supercritical conditions and their reversion when leaving the supercritical state. However, using a common disperse dye of the 9,10-anthraquinone family (Disperse Blue, DB-134) without the addition of co-solvent, only a moderate colour change was obtained for the interior of small wood cuboids (1 cm × 1 cm x 2 cm) even after extensive variation of scCO2 process conditions. Insufficient solubility of the dye in scCO2 was assumed to be a major hindrance for homogeneous wood dyeing. Therefore, we synthesized a variety of 1-n-butylamino- and 1,4-bis(n-butylamino)-9,10-anthraquinone derivatives carrying different alkyl moieties in 2-position, which was confirmed to improve scCO2 solubility. Instead of a previously reported seven-step synthesis affording moderate yields only (60% on average), we propose an alternate much simpler synthesis comprising of Marschalk alkylation (2-position) and a sequence of tosylation and n-alkylamination (1-position). The latter proved to pave way to a wide variety of colours and disperse dyes of improved solubility in scCO2. Moreover, all products were characterized by various techniques including liquid-state 1H and 13C NMR and X-ray crystallography. Complementing X-ray diffraction, quantum-mechanical simulations were performed to predict or confirm conformation and colour of selected compounds.
- Jaxel, Julien,Amer, Hassan,Bacher, Markus,Roller, Alexander,Guggenberger, Matthias,Zwirchmayr, Nele Sophie,Hansmann, Christian,Liebner, Falk
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- Solvent blue 35 of a kind of preparation method
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The invention discloses a method for preparing solvent blue 35. The method comprises the following steps: adding ethanol, anhydrous sodium sulfate, 1,4-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone leuco, acetic acid and n-butylamine into a reactor, closing the reactor, heating to a refluxing temperature, reacting under a pressure of 0.08Mpa or less for 1-4h, distilling off an ethanol and n-butylamine mixed solvent, adding alkaline water to realize separation, filtering, washing, drying, and discharging. In the invention, acetic acid is used as a catalyst, anhydrous sodium sulfate is used as a water absorbing agent, and 1,4-dihydroxyanthraquinone is mixed with the 1,4-dihydroxyanthraquinone leuco in reasonable proportion, so the reaction speed is improved, and the yield is improved; and ethanol is adopted as a solvent to reduce the generation of tar, and a recovered ethanol and n-butylamine mixed solution can be directly used after dehydration in order to reduce the generation of wastewater.
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Paragraph 0019-0020
(2017/03/23)
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- Synthesis of new cytotoxic aminoanthraquinone derivatives via nucleophilic substitution reactions
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Aminoanthraquinones were successfully synthesized via two reaction steps. 1,4-Dihydroxyanthraquinone (1) was first subjected to methylation, reduction and acylation to give an excellent yield of anthracene-1,4-dione (3), 1,4-dimethoxyanthracene- 9,10-dione (5) and 9,10-dioxo-9,10-dihydroanthracene-1, 4-diyl diacetate (7). Treatment of 1, 3, 5 and 7 with BuNH2 in the presence of PhI(OAc)2 as catalyst produced seven aminoanthraquinone derivatives 1a, b, 3a, and 5a-d. Amination of 3 and 5 afforded three new aminoanthraquinones, namely 2-(butylamino)anthracene-1,4-dione (3a), 2-(butylamino)anthracene-9,10-dione (5a) and 2,3-(dibutylamino)anthracene-9,10-dione (5b). All newly synthesised aminoanthraquinones were examined for their cytotoxic activity against MCF-7 (estrogen receptor positive human breast) and Hep-G2 (human hepatocellular liver carcinoma) cancer cells using MTT assay. Aminoanthraquinones 3a, 5a and 5b exhibited strong cytotoxicity towards both cancer cell lines (IC50 1.1-13.0 μg/mL).
- Nor, Siti Mariam Mohd,Sukari, Mohd Aspollah Hj Md,Azziz, Saripah Salbiah Syed Abdul,Fah, Wong Chee,Alimon, Hasimah,Juhan, Siti Fadilah
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p. 8046 - 8062
(2013/08/23)
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- 1,4-Diamino- and 1,4-Dibutylamino-anthraquinones: Reduction and/or Deprotonation-initiated Elimination of the Butyl Groups in Dipolar Aprotic Media
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The standard redox potentials of the one- and two-electron reductions of the title compounds have been determined.The deprotonated form of the dibutylamino compound underwent a base-initiated elimination of the butyl groups and the basicity of the radical anion resulting from one-electron reduction was sufficient to provoke the same type of cleavage through an initial father-son reaction.A multi-step mechanism is proposed for the elimination on the basis of the identification of intermediates.
- Anne, Agnes
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p. 311 - 318
(2007/10/02)
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- (Tosyloxy)anthraquinones: Versatile Synthons for the Preparation of Various Aminoanthraquinones
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Various aminoathraquinones can be easily prepared from (tosyloxy)anthraquinone precursors.Unsymmetrical 1,4-diaminoanthraquinones are prepared via the intermediate monoamino mono(tosyloxy)anthraquinones derived from 1,4-bis(tosyloxy)anthraquinone.The ability to remove tosylate groups sequentially is controlled by the proper selection of solvent and temperature.Hindered 1,4-diamino and 1-aminoanthraquinones are prepared from their corresponding tosyl derivatives, and the amount of steric hindrance present can be succesfully correlated with spectral and color data.The methods described offer advantages over the literature preparations of these compounds.
- Zielske, Alfred G.
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p. 1305 - 1309
(2007/10/02)
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- Novel, Direct Amination of Anthraquinone by Rhodium(I) Complexes
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In the presence of certain rhodium(I) complexes, anthraquinone was found to react with amines to give the 1-alkylaminoanthraquinones, along with small amounts of the 1,4-bis(alkylamino)anthraquinones; this direct amination characteristically occurs only at the α-position of anthraquinone.
- Mita, Katsuhisa,Yamagishi, Takamichi,Hida, Mitsuhiko
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p. 1036 - 1037
(2007/10/02)
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