- Solvent-free synthesis of 4,4-diaminotriarylmethanes-leuco malachite materials in the presence of FePO4
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A fast, efficient and versatile route for the synthesis of 4,4-diaminotriarylmethanes is reported using N,N-dimethyl aniline and aryl aldehydes in presence of FePO4 under solvent-free condition at 100°C.
- Behbahani, Farahnaz K.,Khademloo, Elham
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Read Online
- The novel two step synthesis of CuO/ZnO and CuO/CdO nanocatalysts for enhancement of catalytic activity
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In the present investigation, Copper oxide (CuO)/Zinc oxide (ZnO) and CuO/cadmium oxide (CdO) nanocomposites (NCs) were fabricated by a simple two-step process involving co-precipitation technique and hydrothermal approach for the first time. The Powder X-ray Diffraction (PXRD) pattern demonstrates the existence of monoclinic, hexagonal and cubic phase structure of CuO/ZnO and CuO/CdO NCs. The absorption spectrum of the material was obtained via UV–Visible Spectroscopy and the band-gap value is calculated using Tauc's relation as 1.7 eV, 2.8 eV and 2.75 eV respectively for pure, CuO/ZnO and CuO/CdO NCs. The FESEM images gave the spherical and stone-like morphologies in the prepared CuO/ZnO and CuO/CdO NCs. At room temperature, CuO/ZnO and CuO/CdO NCs act as superior catalyst for the reduction of Rhodamine B (RhB) and Malachite Green (MG) dyes and degradation efficiency attained to be 77.26%, 73.15% for RhB and 79.82%, 74.69 for MG, respectively.
- Kumaraguru, K.,Sankaran, A.
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- Metal- And solvent-free synthesis of aniline- And phenol-based triarylmethanes: Via Br?nsted acidic ionic liquid catalyzed Friedel-Crafts reaction
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A beneficial, scalable and efficient methodology for the synthesis of aniline-based triarylmethanes has been established through the double Friedel-Crafts reaction of commercial aldehydes and primary, secondary or tertiary anilines using Br?nsted acidic ionic liquid as a powerful catalyst, namely [bsmim][NTf2]. This protocol was successfully performed under metal- and solvent-free conditions with a broad range of substrates, giving the corresponding aniline-based triarylmethane products in good to excellent yields (up to 99%). In addition, alternative aromatic nucleophiles such as phenols and electron-rich arenes were also studied using this useful approach to achieve a diversity of triarylmethane derivatives in high to excellent yields. This journal is
- Jaratjaroonphong, Jaray,Saeeng, Rungnapha,Senapak, Warapong,Sirion, Uthaiwan,ponpao, nipaphorn
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p. 22692 - 22709
(2021/07/21)
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- Silver-catalyzed tandem 5- And 6-endo-cyclizationsviaconcomitant yne-ol-imine activation: selective entry to 2-aryldihydrofuroquinolines
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A silver(i) catalyzed domino imination-intramolecular biheterocyclization-aromatization cascade has been developed to construct 2-aryl/-heteroaryl dihydrofuroquinolines in moderate to good yield using an aldehyde and unprotected 4-(2-aminophenyl)but-3-yn-1-ol as precursors. Sequential Ag-(i)-induced 5-endo-digcyclization of the yne-ol part and 6-endo-trigcyclization of a proposed Ag-bound imine, followed by aromatization, furnish the furoquinoline derivatives.
- Das, Prasanta,Karmakar, Swastik,Kundu, Sandip
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p. 16112 - 16118
(2021/09/22)
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- Synthesis of Mannich-type derivatives from amides activated by hydrogen bonding with ZnCl2
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The amide group has one of the most significant functionalities found in many natural products. Herein, low-nucleophilic amides are used in a Mannich-type reaction to synthesize N-acyl-protected amine derivatives. A highly efficient synthetic method utilizing simple aldehydes, N-substituted anilines, and amides as substrates was established through a one-pot amide pathway activated by hydrogen bonding between the ZnCl2 and amide under solvent-free conditions. This strategy can be broadly applied to medicinal chemistry. More importantly, compared with the previous Lewis acid catalyzed reaction, we proposed a new application of zinc chloride. This journal is
- Gong, Bozhen,Hu, Zhiyu,Jiang, Guofang,Le, Zhanggao,Xie, Zongbo,Zhu, Zhiqiang
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supporting information
p. 9095 - 9099
(2020/11/30)
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- COMPOSITIONS, METHODS, AND TEST KITS FOR DETERMINING AUTHENTICITY
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The present disclosure provides composition having at least one leuco composition conforming to Formula (I): [in-line-formulae]Ar1Ar2Ar3CH??(I)[/in-line-formulae] wherein Ar2 and Ar3 are independently a carbocyclic aryl or heteroaryl, and Ar1 is selected from the group consisting of: unsubstituted phenyl, electron deficient carbocyclic aryl, and heteroaryl. The present disclosure also provides a method of detecting an authentic composition and test kits for detecting authentic compositions.
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Paragraph 0143-0144
(2019/04/30)
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- LAUNDRY CARE COMPOSITIONS, METHODS, AND TEST KITS FOR DETERMINING AUTHENTICITY
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The present disclosure provides a laundry care composition having at least one laundry care ingredient and at least one leuco composition conforming to Formula (I): [in-line-formulae]Ar1Ar2Ar3CH??(I)[/in-line-formulae] wherein Ar2 and Ar3 are independently a carbocyclic aryl or heteroaryl, and Ar1 is selected from the group consisting of: unsubstituted phenyl, electron deficient carbocyclic aryl, and heteroaryl. The present disclosure also provides a method of determining an authentic laundry care composition and test kits for detecting authentic laundry care compositions.
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Paragraph 0174-0177
(2019/04/29)
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- Synthesis of symmetric triarylmethane derivatives catalyzed by AIL ionic liquid
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Abstract: An efficient, eco-friendly ionic liquid was described for the synthesis of symmetric triarylmethane derivatives via Baeyer condensation of N,N-dimethylaniline with different active aromatic aldehyde compounds using amide ionic liquid as a catalyst. The syntheses were achieved for the first time using amide ionic liquid as a catalyst eliminating the need for a volatile organic solvent. The advantages of this ionic liquid are low cost and operational simplicity.
- Kang, Li Q.,Gao, Han,Cai, Yue Q.
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- Di- and triarylmethylium ions as probes for the ambident reactivities of carbanions derived from 5-benzylated Meldrum's acid
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The kinetics of the reactions of carbocations with carbanions 1 derived from 5-benzyl-substituted Meldrum's acids 1-H (Meldrum's acid=2,2-dimethyl-1,3- dioxane-4,6-dione) were investigated by UV/Vis spectroscopic methods. Benzhydryl cations Ar2CH+ added exclusively to C-5 of the Meldrum's acid moiety. As the second-order rate constants (kC) of these reactions in DMSO followed the linear free-energy relationship lg k=s N(N+E), the nucleophile-specific reactivity parameters N and s N for the carbanions 1 could be determined. In contrast, trityl cations Ar3C+ reacted differently. While tritylium ions of low electrophilicity (E-2) reacted with 1 through rate-determining β-hydride abstraction, more Lewis acidic tritylium ions initially reacted at the carbonyl oxygen of 1 to form trityl enolates, which subsequently reionized and eventually yielded triarylmethanes and 5-benzylidene Meldrum's acids by hydride transfer.
- Chen, Xi,Tan, Yue,Berionni, Guillaume,Ofial, Armin R.,Mayr, Herbert
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supporting information
p. 11069 - 11077
(2014/10/15)
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- Solvent-free Br?nsted acid catalysed alkylation of arenes and heteroarenes with benzylic alcohols
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A simple and efficient alkylation of aromatic and heteroaromatic compounds via the direct SN1-type nucleophilic substitution of benzylic alcohols in the presence of catalytic amounts of the strong Br?nsted acid o-benzenedisulfonimide under neat conditions is herein reported. A library of di- and triaryl (and heteroaryl) methanes was prepared in good yields and high regioselectivity. The observed reactivity was shown to be in agreement with Mayr's nucleophilicity and electrophilicity scales.
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano,Rucci, Marta,Spano, Giulia,Venturello, Paolo
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p. 1818 - 1826
(2014/03/21)
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- Efficient synthesis of Bis(4-Dimethaminophenyl)arylmethanes and Bis(4-Diamethaminophenyl)alkanes using iodine reagent
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A novel synthetic utility of NaICl2 for the preparation of bis(4-dimethaminophenyl)arylmethanes and bis(4-dimethaminophenyl)alkanes is described. In the presence of an aqueous solution of NaICl2, the reaction of arenes with aromatic aldehydes gives corresponding triarylmethane derivatives regioselectively in moderate to good yields. The method is also useful for the preparation of diarylalkane derivatives by using aliphatic aldehydes. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
- Bachhav, Harshal M.,Takale, Balaram S.,Telvekar, Vikas N.
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p. 1909 - 1914
(2013/05/21)
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- Towards a comprehensive hydride donor ability scale
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Rates of hydride transfer from several hydride donors to benzhydrylium ions have been measured at 20 °C and used for the determination of empirical nucleophilicity parameters N and sN according to the linear free energy relationship log k20 °C=sN(N+E). Comparison of the rate constants of hydride abstraction by tritylium ions with those calculated from the reactivity parameters sN, N, and E showed fair agreement. Therefore, it was possible to convert the large number of literature data on hydride abstraction by tritylium ions into N and sN parameters for the corresponding hydride donors, and construct a reactivity scale for hydride donors covering more than 20 orders of magnitude.
- Horn, Markus,Schappele, Ludwig H.,Lang-Wittkowski, Gabriele,Mayr, Herbert,Ofial, Armin R.
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supporting information
p. 249 - 263
(2013/02/25)
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- Halogen-free room-temperature bronsted acidic ionic liquid [Hmim]+ HSO4- as a recyclable green "dual reagent" catalysis for the synthesis of triarylmethanes (TRAM s) ;
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The halogen-free Brnsted acidic ionic liquid methylimidazolium hydrogen sulfate ([Hmim]+ HSO4-) acts as a very efficient catalyst for the one-pot, two-component Baeyer condensation of a variety of aromatic aldehydes with dimethyl or diethyl aniline at room temperature. This green reagent behaves as both catalyst and solvent; that is, it exhibits dual-reagent catalysis. The room-temperature acidic ionic liquid could be recycled several times with almost no loss in the yield of the reaction. This is the first report of the Baeyer synthesis with a halogen-free ionic liquid.
- Mukhopadhyay, Chhanda,Datta, Arup,Tapaswi, Pradip Kumar
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experimental part
p. 2453 - 2463
(2012/06/29)
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- Real-time kinetics of surfactant molecule transfer between emulsion particles probed by in situ second harmonic generation spectroscopy
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Emulsions are widely used in industrial and environmental remediation applications. The breaking and reformulation of emulsions, which occur during their use, lead to changes in their surface composition as well as their physical and chemical properties. Hence, a fundamental understanding of the transfer of surfactant molecules between emulsion particles is required for optimization of their applications. However, such an understanding remains elusive because of the lack of in situ and real-time surface-specific techniques. To address this, we designed and synthesized the surfactant probe molecules MG-butyl-1 (2) and MG-octyl-1 (3), which contain an n-butyl and an n-octyl chain, respectively, and a charged headgroup similar to that in malachite green (MG, 1). MG is known to be effective in generating second harmonic generation (SHG) signals when adsorbed onto surfaces of colloidal microparticles. Making use of the coherent nature of SHG, we monitored in real-time the transfer of 2 and 3 between oil-in-water emulsion particles with diameters of ～220 nm. We found that 3 is transferred ～600 times slower than 2, suggesting that an increase in the hydrophobic chain length decreases the transfer rate. Our results show that SHG combined with molecular design and synthesis of surfactant probe molecules can be used to measure the rate of surfactant transfer between emulsion particles. This method provides an experimental framework for examining the factors controlling the kinetics of surfactant transfer between emulsion particles, which cannot be readily investigated in situ and in real-time using conventional methods.
- You, Yumeng,Bloomfield, Aaron,Liu, Jian,Fu, Li,Herzon, Seth B.,Yan, Elsa C. Y.
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supporting information; experimental part
p. 4264 - 4268
(2012/04/10)
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- SbCl3-catalyzed one-pot synthesis of 4,4′-diamino- triarylmethanes under solvent-free conditions: Synthesis, characterization, and DFT studies
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A simple, efficient, and mild procedure for a solvent-free one-step synthesis of various 4,4′-diaminotriarylmethane derivatives in the presence of antimony trichloride as catalyst is described. Triarylmethane derivatives were prepared in good to excellent yields and characterized by elemental analysis, FTIR, 1H and 13C NMR spectroscopic techniques. The structural and vibrational analysis were investigated by performing theoretical calculations at the HF and DFT levels of theory by standard 6-31Gs *, 6-31G*/B3LYP, and B3LYP/cc-pVDZ methods and good agreement was obtained between experimental and theoretical results.
- Bardajee, Ghasem Rezanejade
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experimental part
p. 135 - 144
(2011/05/16)
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- Resonance rayleigh scattering, second-order scattering and frequency doubling scattering methods for the determination of malachite green in aquatic products
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In presence of the HOAc-NaOAc buffer solution and heating condition, leucomalachite green (LMG) can reacts with I3- to form an ionassociation complex. It made a significant enhancement of resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency doubling scattering (FDS). The increments of scattering intensity (DI) were directly proportional to the concentration of leucomalachite green in a certain range. The detection limits were 1.2 ng mL-1 for resonance Rayleigh scattering method, 1.5 ng mL-1 for second-order scattering method and 1.5 ng mL-1 for frequency doubling scattering method, respectively. This result indicates that these methods exhibited high sensitivities. And they were simple and feasible. Three new highly sensitive and simple methods of determination leucomalachite green have been developed. With the reducing action of potassium borohydride, over 85 % of malachite green (MG) can be converted to leucomalachite green. So these can be applied to determine the malachite green in aquatic products.
- Zou, Yan,Geng, Weidong,Liu, Mousheng,Yang, Yaling
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experimental part
p. 5275 - 5279
(2012/07/02)
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- ZrOCl2 catalyzed Baeyer condensation: A facile and efficient synthesis of triarylmethanes under solvent-free conditions
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A facile and efficient synthesis of an array of triarylmethanes by the Baeyer condensation of different arylaldehydes carrying activated and deactivated groups and N,N-dimethyIaniline using a catalytic amount of ZrOCI2 under solvent-free microwave irradiation conditions is described. Further, the catalytic activity of ZrOCI2 is compared with traditional Lewis acid catalysts and found that this synthetic method has the advantages of excellent yields (70-96%), shorter reaction time (few minutes) and solvent-free conditions.
- Reddy, Ch Sanjeeva,Nagaraj,Srinivas,Reddy
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experimental part
p. 248 - 254
(2009/12/03)
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- Hydride-donor abilities of 1,4-dihydropyridines: A comparison with π nucleophiles and borohydride anions
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(Chemical Equation Presented) How are dihydropyridines like indoles? Both groups of compounds have similar nucleophilicity parameters N and are therefore suitable substrates for iminium-catalyzed reactions of α,β- unsaturated aldehydes. The N parameters of 1,4-dihydropyridines were derived from the rates of hydride transfer reactions to benzhydrylium ions (see scheme).
- Richter, Dorothea,Mayr, Herbert
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supporting information; experimental part
p. 1958 - 1961
(2009/07/25)
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- GLUCOCORTICOID-SELECTIVE ANTI-INFLAMMATORY AGENTS
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Compounds having Formula (I) are useful for modulating the glucocorticoid receptor in a mammal. Also disclosed are pharmaceutical compositions comprising compounds of Formula (I) and methods of treating immune, autoimmune, inflammatory, adrenal imbalance, cognitive and behavioral diseases in a mammal.
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Page/Page column 20
(2010/02/08)
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- Baeyer condensation in chloroaluminate ionic liquid
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1-n-butylpyridinium chloroaluminate serves the dual purpose of a reaction medium and a Lewis acid catalyst for condensation of substituted benzaldehydes with N, N-dimethylaniline to obtain triarylmethanes (leuco bases) in good yields with significant reduction in reaction time and simplification of the workup process.
- Paul, Aniruddha M.,Khandekar, Amit C.,Khadilkar, Bhushan M.
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p. 168 - 169
(2007/10/03)
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- Synthesis and characterization of N-demethylated metabolites of malachite green and leucomalachite green
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Malachite green (MG), a triphenylmethane dye used to treat fungal and protozoan infections in fish, undergoes sequential oxidation to produce various N-demethylated derivatives (monodes-, dides(sym)-, dides(unsym)-, trides-, and tetrades-) both before and after reduction to leucomalachite green (LMG). The close structure resemblance of the metabolites with aromatic amine carcinogens implicates a potential genotoxicity from exposure to MG. The availability of the synthetic standards is important for metabolic and DNA adduct studies of MG. This paper describes a simple and versatile method for the synthesis of MG, LMG, and their N-demethylated metabolites. The synthesis involves a coupling of 4-(dimethylamino)-benzophenone or 4-nitrobenzophenone with the aryllithium reagents derived from appropriately substituted 4-bromoaniline derivatives, followed by treatment with HCl in methanol. The resulting cationic MG and their leuco analogues showed systematic UV/vis spectral and tandem mass fragmentation patterns consistent with sequential N-demethylation. The extensive 1H and 13C spectral assignments of the metabolites were aided by the availability of 13C7-labeled MG and LMG. The results indicate the existence of a resonance structure with the cationic charge located in the central methane carbon (C7). The synthetic procedure is general in scope so that it can be extended to the preparation of N-demethylated metabolites of other structurally related N-methylated triphenylmethane dyes.
- Cho, Bongsup P.,Yang, Tianle,Blankenship, Lonnie R.,Moody, Joanna D.,Churchwell, Mona,Beland, Frederick A.,Culp, Sandra J.
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p. 285 - 294
(2007/10/03)
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- Glucocortiocoid-selective agents
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Compounds having Formula I are useful for modulating the glucocorticoid receptor in a mammal. Also disclosed are pharmaceutical compositions comprising compounds of Formula I and methods of treating immune, autoimmune, inflammatory, adrenal imbalance, cognitive and behavioral diseases in a mammal.
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- Montmorillonite clay catalysis VI: Synthesis of triarylmethanes via Baeyer condensation of aromatic aldehydes with N,N-dimethylaniline catalysed by montmorillonite K-10
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Triarylmethanes are synthesized in good to excellent yield via Baeyer condensation of aromatic aldehydes with N,N-dimethylaniline catalysed by montmorillonite K 10 at 100°C in the absence of solvent.
- Zhang, Zhan-Hui,Yang, Feng,Li, Tong-Shuang,Fu, Cheng-Guang
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p. 3823 - 3828
(2007/10/03)
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- INDEPENDENT SYNTHESIS OF THREE TYPES OF N-SUBSTITUTED DIHYDROPYRIMIDINES AND THEIR REACTIONS WITH MALACHITE GREEN
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Pyrimidine-2(1H)-thiones and their corresponding dihydroderivatives were treated with Raney nickel to afford respectively three types of dihydropyrimidine isomers, which reacted with malachite green in similar rate constants to 1-benzyl-1,4-dihydronicotinamide.
- Kashima, Choji,Shimizu, Masao,Katoh, Akira,Omote, Yoshimori
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p. 209 - 212
(2007/10/02)
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- Action of Sodium Dithionite on Some Cationic Dyes
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Sodium dithionite (SDT) has been developed as a useful reagent to dequaternize a variety of cationic dyes.Triarylmethane dyes are converted into leuco bases; however, hemicyanines smoothly undergo dehydrochlorination.Phenothiazine and phenoxazine dyes on reduction with SDT give unstable leuco bases, which can be isolated as their N-benzoyl derivatives.The IR, PMR and mass spectral studies of the leuco bases or the dequaternized products have been found to be useful for structure elucidation of the cationic dyes.
- Ayyangar, N. R.,Khanna, I. K.
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p. 763 - 766
(2007/10/02)
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- Etudes sur les composes gem-diamines-V-Reactions d'anilines sur des composes gem-dimorpholines.
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A systematic study of gem-dimorpholino compounds, which produce aldehydes by hydrolysis, has shown that such compounds do indeed have aldehydic character and can be used in synthesis in place of the corresponding aldehydes.As part of this study we have examined the behaviour of such gem-dimorpholino compounds towards some nucleophilic reagents such as mercaptans, amides and anilines under acid conditions.We have found experimental conditions under which symmetrical geminal compounds are produced: dithioacetals, gem-bis(acylamino), gem-diamino and gem-diaryl compounds.We have thus developed several new synthetic methods which compare favourably with existing methods.In most cases we have been able to show that the reaction proceeds by an intermediate in which only one of the morpholino groups has been replaced by the nucleophile.In this paper we report on the condensation of some anilines with gem-dimorpholino compounds.N,N-dimethylaniline condenses with gem-dimorpholino compounds as with the corresponding aldehydes to give gem-diaryl compounds.The case of primary arylamines is remarkable for the different results obtained.As could be expected from our most recent results, most of the condensation products are complex mixtures which are either non-distillable and non-crystallisable oils or glassy solids with indistinct melting points.It is often impossible to isolate any pure chemical substance from these mixtures.We shall thus only describe certain cases: the behaviour of 2,6-xylidine is particularly interesting.Under certain conditions this aniline derivative can condense on the aromatic ring similarly to N,N-dimethylaniline.The initial product of the reaction is an aldimine or "anil".Benzaldimines which are stabilised by conjugation do not react further while phenylglyoxaldimines are transformed into gem-diaryl compounds by heating in acetic acid. 2,5-dimethoxyaniline also condenses by way of the aromatic ring to give a gem-diaryl compound but the corresponding aldimine could not be shown to be an intermediate. 2-nitro and 3-nitroaniline, in which the aromatic ring is deactivated, can only condense by the nitrogen atom to give gem-diamino compounds.In summary, we think that primary arylamines in acetic acid condense with gem-dimorpholino compounds preferentially on the nitrogen atom of the amino group.These compounds can subsequently, according to their stability, rearrange provided that the aromatic ring is activated by electron-donating substituents.It still remains to be determined if there is a definite point at which a primary aniline starts to act as an ambifunctional nucleophile.
- Floc'H, Yves Le,Morvan, Jean-Marcel,Brault, Auguste
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p. 157 - 162
(2007/10/02)
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