121-14-2Relevant articles and documents
Fluoropolymer-Coated PDMS Microfluidic Devices for Application in Organic Synthesis
Yang, Tianjin,Choo, Jaebum,Stavrakis, Stavros,de Mello, Andrew
, p. 12078 - 12083 (2018)
In recent years there has been huge interest in the development of microfluidic reactors for the synthesis of small molecules and nanomaterials. Such reaction platforms represent a powerful and versatile alternative to traditional formats since they allow for the precise, controlled, and flexible management of reactive processes. To date, the majority of microfluidic reactors used in small-molecule synthesis have been manufactured using conventional lithographic techniques from materials such as glasses, ceramics, stainless steel, and silicon. Surprisingly, the fabrication of microfluidic devices from such rigid materials remains ill-defined, complex, and expensive. Accordingly, the microfluidic toolkit for chemical synthesis would significantly benefit from the development of solvent-resistant microfluidic devices that can be manufactured using soft-lithographic prototyping methods. Whilst significant advances in the development of solvent-resistant polymers have been made, only modest steps have been taken towards simplifying their use as microfluidic reactors. Herein, we emphasize the benefits of using a commercially available, amorphous perfluorinated polymer, CYTOP, as a coating with which to transform PDMS into a chemically inert material for use in organic synthesis applications. Its efficacy is demonstrated through the subsequent performance of photooxidation reactions and reactions under extremely acidic or basic conditions.
Urea nitrate and nitrourea: powerful and regioselective aromatic nitration agents
Almog, Joseph,Klein, Asne,Sokol, Anat,Sasson, Yoel,Sonenfeld, Dana,Tamiri, Tsippy
, p. 8651 - 8652 (2006)
Urea nitrate (UN) and nitrourea (NU), easily prepared from urea and nitric acid, convert deactivated aromatic compounds to the corresponding nitrated derivatives with a high yield and a high regioselectivity under very mild conditions. The performance of the two reagents is quite similar indicating that NU is an intermediate in the UN nitration process.
Control over m-nitrotoluene concentration in products of heterogeneous mononitration of toluene
Artemov,Tselinskii,Kukushkin,Filatova,Ashikhin
, p. 2063 - 2072 (2007)
Heterogeneous mononitration of toluene with sulfuric-nitric acid mixtures, occurring in the charged interfacial monolayer with high para selectivity, was studied. Ways to suppress the meta substitution in the toluene mononitration stage by controlling the nitrating mixture composition, process parameters, and catalytic additives were found.
The efficacy of 'Claycop' in the dinitration of toluene
Lancaster, N. Llewellyn,Moodie, Roy B.,Sandall, John P. B.
, p. 847 - 848 (1997)
Claycop and acetic anhydride in tetrachloromethane are modestly catalytic and regioselective in the mononitration of toluene, but are neither catalytic nor regioselective in the nitration of 2-nitrotoluene.
Regioselective double Kyodai nitration of toluene and chlorobenzene over zeolites. High preference for the 2,4-dinitro isomer at the second nitration stage
Peng, Xinhua,Suzuki, Hitomi
, p. 3431 - 3434 (2001)
(matrix presented) The Kyodai nitration of toluene and chlorobenzene has been examined in the presence of a solid inorganic catalyst (montmorillonite K10, zeolite HZSM-5, or HBEA-25). Regioselection was quite low at the mononitration stage, but a considerably high preference for the 2,4-isomer was observed at the dinitration stage.
Copper-cobalt synergy in Cu1-xCoxFe2O4 spinel ferrite as a highly efficient and regioselective nanocatalyst for the synthesis of 2,4-dinitrotoluene
Fareghi-Alamdari, Reza,Zandi, Farzad,Keshavarz, Mohammad Hossein
, p. 71911 - 71921 (2015)
Highly regioselective dinitration of toluene with nitric acid as nitrating agent in the presence of Cu1-xCoxFe2O4 (0 ≤ x ≤ 1) as nanocatalysts is described. The results of this protocol show that this nitration system can significantly improve the selectivity and the yield of 2,4-dinitrotoluene. The prepared spinel ferrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). Copper and cobalt synergy (50%:50%) in spinel ferrite also shows the best catalytic activity in the selectivity of dinitrotoluene under solvent-free conditions.
Heterophase nitration of o-nitrotoluene with sulfuric-nitric acid mixtures of low nitrating activity in gas-containing emulsions
Artemov,Veretennikov,Tselinskii
, p. 1871 - 1877 (2007)
Heterophase nitration of o-nitrotoluene, in which an increase in the contribution of the reaction in the boundary adsorption monolayer under conditions of surface aeration leads to a higher yield of 2,4-dinitrotoluene and larger 2,4-/2,6-dinitrotoluene isomer ratio, was studied.
Hafnium(IV) and zirconium(IV) triflates as superior recyclable catalysts for the atom economic nitration of o-nitrotoluene
Waller, Francis J.,Barrett, Anthony G. M.,Braddock, D. Christopher,Ramprasad, Dorai
, p. 1641 - 1642 (1998)
The hydrated group 4 metal triflates, Hf(OTf)4 and Zr(OTf)4, were found to be excellent catalysts (10 mol%) for the mononitration of o-nitrotoluene using a single equivalent of concentrated (69%) nitric acid. The only side product is water and the catalysts are readily recycled from the aqueous phase and re-used.
Zeolite catalysis of aromatic nitrations with dinitrogen pentoxide
Claridge, Robert P.,Lancaster, N. Llewellyn,Millar, Ross W.,Moodie, Roy B.,Sandall, John P. B.
, p. 1815 - 1818 (1999)
The reactions of 2-nitrotoluene. 1-chloro-2-nitrobenzene, and 1-chloro-4-nitrobenzene with dinitrogen pentoxide in dichloromethane at 0 °C are strongly catalysed by some zeolites notably H-Faujasite-720, catalysis by which is investigated in detail. Yields of the nitrated aromatics are near-quantitative. In the first two substrates nitration occurs more regioselectively at the 4-position compared to the uncatalysed reaction. The reaction of 1-chloro-2-nitrobenzene shows a kinetic form which is close to first-order with a rate-constant independent of the concentration Of N2O5 and proportional to the mass of zeolite. Initial addition of the major product, 1-chloro-2,4-dinitrobenzene, causes rate-inhibition. Mechanisms are discussed.
Competition between electron-donor and electron-acceptor substituents in nitrotoluene isomers: A photoelectron spectroscopy and ab initio investigation
Rondino, Flaminia,Catone, Daniele,Mattioli, Giuseppe,Bonapasta, Aldo Amore,Bolognesi, Paola,Casavola, Anna Rita,Coreno, Marcello,O'Keeffe, Patrick,Avaldi, Lorenzo
, p. 5272 - 5282 (2014)
We present an investigation of the close relationship between chemical structure, physical properties and reactivity of the three nitrotoluene isomers: a joint experimental and theoretical study, based on X-ray photoelectron spectroscopy (XPS) measurements and ab initio calculations, addressing the complex interplay between the competing electron-donor and electron-acceptor effects of the nitro- and methyl-substituents on the chemical properties of the nitrotoluene isomers. As the main results of the investigation we: (i) point out that accurate ab initio calculations play a key role in the complete assignment of photoemission measurements, as well as in the estimate of proton affinities in the case of all the eligible sites; (ii) revisit, at a more quantitative level, textbook models based on inductive and resonant effects of different substituents of the aromatic ring, as well as on the hyper-conjugative connection of the methyl group to the π-conjugated system; (iii) provide an accurate analysis of correlation patterns between calculated proton affinities and core-ionization energies, which represent a powerful tool, capable of predicting site-specific reactivities of polysubstituted molecules in the case of electrophilic aromatic substitution reactions.