36663-09-9Relevant academic research and scientific papers
Reactions of Halogenomethanes in the Vapour Phase. Part 5. The Reactions of Imidazolines, Anils, and 1-Methylimidazole with Chloroform at 550 deg C, and a Comparison with their Liquid-Phase Reactions with Trichloroacetate Ion or Hexachloroacetone and Base
Busby, Reginald E.,Khan, Mohammad A.,Khan, Mohammad R.,Parrick, John,Shaw, C. J. Granville
, p. 1431 - 1435 (1980)
The vapor-phase reactions of imidazolines and anils with chloroform at 550 deg C are compared with their liquid-phase reactions in the presence of hexachloroacetone and base or upon thermolysis with trichloroacetate ion.In the vapour-phase reactions imidazolines, unlike imidazoles, gave non-chlorinated pyrimidines, and 1-methyl-imidazole gave 2-cyanopyrrole and the four 3-chlorocyanopyridines.
Solvent-freeN-Boc deprotection byex situgeneration of hydrogen chloride gas
De Borggraeve, Wim M.,Gilles, Philippe,Van Mileghem, Seger,Verschueren, Rik H.
, p. 5782 - 5787 (2021/07/12)
An efficient, scalable and sustainable method for the quantitative deprotection of thetert-butyl carbamate (N-Boc) protecting group is described, using down to near-stoichiometric amounts of hydrogen chloride gas in solvent-free conditions. We demonstrate theex situgeneration of hydrogen chloride gas from sodium chloride and sulfuric acid in a two-chamber reactor, introducing a straightforward method for controlled and stoichiometric release of HCl gas. The solvent-free conditions allow deprotection of a wide variety ofN-Boc derivatives to obtain the hydrochloride salts in quantitative yields. The procedure obviates the need for any work-up or purification steps providing an uncomplicated green alternative to standard methods. Due to the solvent-free, anhydrous conditions, this method shows high tolerance towards acid sensitive functional groups and furnishes expanded functional group orthogonality.
Direct Amidation of Esters by Ball Milling**
Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
supporting information, p. 21868 - 21874 (2021/09/02)
The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
Selective and Additive-Free Hydrogenation of Nitroarenes Mediated by a DMSO-Tagged Molecular Cobalt Corrole Catalyst
Sch?fberger, Wolfgang,Timelthaler, Daniel,Topf, Christoph
supporting information, p. 2114 - 2120 (2021/07/22)
We report on the first cobalt corrole that effectively mediates the homogeneous hydrogenation of structurally diverse nitroarenes to afford the corresponding amines. The given catalyst is easily assembled prior to use from 4-tert-butylbenzaldehyde and pyrrole followed by metalation of the resulting corrole macrocycle with cobalt(II) acetate. The thus-prepared complex is self-contained in that the hydrogenation protocol is free from the requirement for adding any auxiliary reagent to elicit the catalytic activity of the applied metal complex. Moreover, a containment system is not required for the assembly of the hydrogenation reaction set-up as both the autoclave and the reaction vessels are readily charged under a regular laboratory atmosphere.
Cobalt-Catalyzed Deoxygenative Hydroboration of Nitro Compounds and Applications to One-Pot Synthesis of Aldimines and Amides
Gudun, Kristina A.,Hayrapetyan, Davit,Khalimon, Andrey Y.,Segizbayev, Medet,Slamova, Ainur,Zakarina, Raikhan
, (2021/11/30)
The commercially available and bench-stable Co(acac)2 ligated with bis[(2-diphenylphosphino)phenyl] ether (dpephos) was employed for selective room temperature hydroboration of nitro compounds with HBPin (TOF up to 4615 h?1), tolerating halide, hydroxy, amino, ether, ester, lactone, amide and heteroaromatic functionalities. These reactions offered a direct access to a variety of N-borylamines RN(H)BPin, which were in situ treated with aldehydes and carboxylic acids to produce a series of aldimines and secondary carboxamides without the need for dehydrating and/or coupling reagents. Combination of these transformations in a sequential one-pot manner allowed for direct and selective synthesis of aldimines and secondary carboxamides from readily available and inexpensive nitro compounds.
Synthesis, characterization and electropolymerization of functionalized organic salt–anilinium saccharinate and electrochemically controlled release of saccharinate anions
Shen, Lanbo,Gao, Na,Huang, Xirong
, (2019/11/03)
In this work, a novel functionalized organic salt ? anilinium saccharinate ([HANI][Sac]) was synthesized by the ion exchange method, and its composition and properties were characterized by 1H NMR, 13C NMR, ESI/MS and TG-DSC techniques. [HANI][Sac] can be used as both monomer and supporting electrolyte for efficient electrosynthesis of polyaniline (PANI) in acetonitrile. The obtained PANI has hierarchical porous structure and its doping degree with saccharinate anion ([Sac]-) is as high as 33.5%. The resulting [Sac]--doped-PANI (PANI-[Sac]) can be used as an electrochemically controlled drug delivery system. The in vitro release kinetics of [Sac]- under different potential stimuli conditions showed that, at a given time, the release rate of [Sac]- and its release percentage (ratio of the amount released to that loaded) increase with the negative shift of the applied potential. The amount of [Sac]- loaded and/or released can also be regulated by varying the charge for PANI electropolymerization. The present work provides a new strategy for the facile construction of conducting polymer-based electrochemically controlled drug release system.
METHOD FOR PREPARING AN AMINE HYDROCHLORIDE SUSPENSION
-
Paragraph 0093, (2020/12/25)
The invention relates to a method for preparing a suspension of a hydrochloride of an organic amine, comprising the following steps of (i) initially charging at least one organic solvent in a reaction vessel to form a liquid level, (ii) adding hydrogen chloride, (iii) adding the organic amine, wherein the organic amine is added below the liquid level present in the reaction vessel and steps (ii) and (iii) are at least partly carried out simultaneously. Furthermore, the present invention also relates to a method wherein the suspension obtained after step (iii) is reacted in a step (iv) with phosgene to obtain the organic isocyanate corresponding to the organic amine used, to the corresponding organic isocyanate and to the use of the organic isocyanate for producing polyisocyanates.
Preparation and application methods for ionic liquid inhibitor used for water-based drilling fluid
-
Paragraph 0019-0020, (2019/03/26)
The invention discloses preparation and application methods for an ionic liquid inhibitor used for a water-based drilling fluid. The preparation method comprises the following steps: (1) allowing a cation raw material to react with concentrated acid so as to generate corresponding salt, wherein the cation raw material is one selected from the group consisting of alkylamine, phenol and aniline, andthe concentrated acid is one selected from the group consisting of concentrated hydrochloric acid and concentrated phosphoric acid; and (2) allowing the salt to react with an anion raw material in asolvent so as to obtain a target ionic liquid inhibitor, wherein the anion raw material is one selected from the group consisting of AlCl3, FeCl3 and ZnCl2, or a salt containing one group selected from the group consisting of RCOO- and SbF6-. The ionic liquid inhibitor provided by the invention has good compatibility with a drilling fluid and excellent inhibition performance; under the same conditions, the recovery rate of the ionic liquid inhibitor is 39% higher compared with clear water and 13% higher compared with KCl slurry having a concentration of 5%; and the ionic liquid inhibitor is close to an amine-based inhibitor and free of the problem of generation of foam.
Cyclometalated Ruthenium(II) NHC Complexes with Imidazo[1,5-a]pyridine-Based (C^C*) Ligands – Synthesis and Characterization
Schleicher, David,Tronnier, Alexander,Soellner, Johannes,Strassner, Thomas
, p. 1956 - 1965 (2019/03/07)
We present the synthesis and characterization of cyclometalated ruthenium(II) NHC complexes with phenyl-substituted imidazo[1,5-a]pyridine C^C* ligands. The corresponding p-cymene complexes can be reacted with bipyridine to form bisheteroleptic ruthenium(II) dyes. The compounds have been characterized by one- and two-dimensional 1H/13C NMR spectroscopy, elemental analysis, cyclic voltammetry, infrared spectroscopy, as well as solid-state structure (X-ray) analysis.
Formal Aniline Synthesis from Phenols through Deoxygenative N-Centered Radical Substitution
Lardy, Samuel W.,Luong, Kristine C.,Schmidt, Valerie A.
supporting information, p. 15267 - 15271 (2019/12/11)
Phenolic, lignin-derived substrates have emerged as desirable biorenewable chemical feedstocks for coupling reactions. A radical-mediated conversion of phenol derivatives to anilines is reported, using unfunctionalized hydroxamic acids as the N-centered radical source. The applicability of this triethyl phosphite mediated O-atom transfer approach, which tolerates a range of steric and electronic demands to naturally occurring phenols and lignin models, has been demonstrated in this work to access the corresponding aniline derivatives.
