142-04-1Relevant articles and documents
Synthesis of N-Aryl-3,5-dichloro-4H-1,2,6-thiadiazin-4-imines from 3,4,4,5-Tetrachloro-4H-1,2,6-thiadiazine
Kalogirou, Andreas S.,Manoli, Maria,Koutentis, Panayiotis A.
, p. 4118 - 4121 (2015)
Condensation of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine with a range of anilines gave 22 N-aryl-3,5-dichloro-4H-1,2,6-thiadiazin-4-imines in 43-96% yields. The scope and limitations of this condensation are briefly investigated. Furthermore, mono- and bis-substitution of the C-3 and C-5 chlorines of 3,5-dichloro-N-phenyl-4H-1,2,6-thiadiazin-4-imine by amine and alkoxide nucleophiles is explored. Finally, Stille coupling chemistry is used to prepare several N-phenyl-3,5-diaryl-4H-1,2,6-thiadiazin-4-imines.
Anilinium dihydrogen phosphate
Kaman, Ondej,Smrcok, Lubomir,Gyepes, Robert,Havlicek, David
, p. o57-o60 (2012)
The triclinic structure of the title compound, C6H 8N+·H2PO4-, with three symmetry-independent structural units (Z′ = 3), is formed of separate organic and inorganic layers alternating along the b axis. The building blocks of the inorganic layer are deformed H2PO4 tetra-hedra assembled into infinite ladders by short and hence strong hydrogen bonds. The anilinium cations forming the organic layer are not hydrogen bonded to one another, but they are anchored by four N-H...O crosslinks between the dihydrogen phosphate chains of adjacent ladders. Two H atoms of each-NH3 group then form one normal and one bifurcated N-H...O hydrogen bond to the P=O oxygens of two tetra-hedra of one chain, while the third H atom is hydrogen bonded to the nearest O atom of an adjacent chain belonging to another dihydrogen phosphate ladder.
Effect of Solvents on Acid-Catalyzed Claisen Amino Rearrangement in N-(1-Methyl-2-butenyl)aniline
Abdrakhmanov,Sharafutdinov,Mustafin,Zimin, Yu. S.,Daminev
, p. 23 - 27 (2019)
Abstract: The effect solvents have on the processes of rearrangement and elimination in N-(1-methyl-2-butenyl)aniline (I) in the presence of HCl is studied. It is shown that the dependence of the rearrangement and elimination rate constants of (I) · HCl on the nature of solvents are described perfectly by the Koppel–Palm equation, which considers both nonspecific and specific solvation. The inhibitory effect of solvent nucleophilicity is explained by the complexation between (I) · HCl and solvent molecules. Analysis of the (I) · HCl conversion products obtained in a mixed solvent (m-toluidine + nitrobenzene) demonstrates the intermolecular transfer of the allyl moiety, confirming the formation of allyl cations in the Claisen amino rearrangement.
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)
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.
Iron-catalyzed selective reduction of nitro compounds to amines
Pehlivan, Leyla,Métay, Estelle,Laval, Stéphane,Dayoub, Wissam,Demonchaux, Patrice,Mignani, Gérard,Lemaire, Marc
, p. 1939 - 1941 (2010)
An efficient reduction of the nitro group with a catalytic amount of Fe(acac)3 and TMDS in THF at 60 °C affording the corresponding amine is described.
Semi-organic salts of aniline with inorganic acids: Prospective materials for the second harmonic generation
Matulková, Irena,Cihelka, Jaroslav,Fejfarová, Karla,Duek, Michal,Pojarová, Michaela,Vank, Pemysl,Kroupa, Jan,ála, Michal,Krupková, Radmila,Němec, Ivan
, p. 4131 - 4138 (2011)
Three novel inorganic salts of aniline with sulfuric and selenic acids were prepared and characterized by X-ray structural analysis. Anilinium(1+) selenate, (C6H5NH3 +) 2SeO4 2-, and anilinium sulfate, (C 6H5NH3 +)2SO 4 2-, crystallize in the monoclinic space group C2. The crystal structures are based on hydrogen bonded layers of alternating anilinium cations and inorganic anions. Anilinium(1+) selenate dihydrate, (C 6H5NH3 +)2SeO 4 2-·2H2O, crystallizes in the monoclinic space group C2/c. The crystal structure is formed by a network of alternating anilinium cations, selenate anions and water molecules connected by a system of intermolecular hydrogen bonds. The FTIR and Raman spectra of all the compounds have been recorded and discussed as well as their crystal structures. According to the DSC curves and temperature dependence of lattice parameters, anilinium sulfate exhibits phase transitions at 217 and 182 K. The appropriate changes of vibrational spectra were also recorded during cooling of the sample especially in the N-H stretching and sulfate antisymmetric stretching (ν3 SO4 2-) spectral regions. The quantitative measurements of the second harmonic generation at 1064 nm were performed using powdered samples of anilinium sulfate, anilinium chloride and anilinium selenate, and the relative efficiencies deff = 0.05dKDP, deff = 2.33dKDP and deff = 0.05dKDP (KDP; i.e. KH 2PO4) have been observed, respectively.
Synthesis and experimental and theoretical characterization of m-fluorosulfinylaniline
Páez Jerez, Ana L.,Chemes, Doly M.,Cutin, Edgardo H.,Oberhammer, Heinz,Robles, Norma L.
, p. 4445 - 4451 (2015)
The synthesis of m-fluorosulfinylaniline together with a tentative assignment of the vibrational, NMR and mass spectra are reported. Quantum chemical calculations predict two stable conformers, with very similar energies, both of which possess in the liquid phase syn structure of the -NSO moiety (syn of the SO double bond relative to the C-N single bond). Both conformers belong to the CS symmetry group and differ by the relative orientation of the fluorine atom and the NSO group. However, the FT-IR, FT-Raman and NMR spectra do not allow a distinction between these two conformers. The experimentally observed spectral data (FT-IR, FT-Raman, 1H and 13C and GC-mass spectrometry) of the title compound are compared with the spectral data obtained by quantum chemical calculations and the gauge including atomic orbital (GIAO) method (DFT/B3LYP approximation using 6-311+G(df), 6-311++G(df,pd) and cc-pVTZ basis sets). Moreover, natural bond orbital (NBO) analysis is applied for studying the stability of the molecule upon charge delocalization in order to provide an explanation of its electronic properties.
Amine Catalysis of the Hydrolysis of Trifluoroacetanilide
Huffman, Robert W.
, p. 2675 - 2680 (1980)
Only hydrolysis products could be isolated from the reaction of trifluoroacetanilide I with aqueous n-butylamine buffer at pH 10.5.Kinetic studies of the decomposition of trifluoroacetanilide I in aqueous morpholine, n-butylamine, piperidine and trimethylamine buffers were also conducted.The most reasonable scheme for the reaction mechanism, compatible with all data, is presented in Scheme I and involves the general-base-catalyzed decomposition of the intermediate III which can be formed by hydroxide ion or water addition to I.Utilizing the constants of Table I, eq 6 is capable of predicting observed rate constants with an error of l ess than 9 percent (see Tables II an III).Some variation in values for these constants for trimethylamine buffers is observed and attributed to possible activity changes for the solutions.Deuterium isotope rate effects were determined for these constants in morpholine buffers.A value of k1H2O/k2D2O of 0.39 was obtained and may indicate the presence of a third pathway for the generation of III (eq 9), involving the hydration of the anion II.A value of k4H2O/k4D2O of 1.65 and a Broensted β value of 0.23 for k4 are interpreted to indicate general-base catalysis by the amine buffer.The low values for these quantities are indicative of a transition state involving an early proton transfer.General-base catalysis of proton transfer for the k4 step is also indicated by the fact that trimethylamine appears to behave mechanistically, similar to the other amines used.The value of 8.8 obtained for k3H2O/k3D2O clearly shows proton transfer to be occuring in this step as well.The results of this study thus support those suggested previously in that the hydrolysis of I undergoes a change in rate-determining step in mild alkaline aqueous solutions.This occurs because of the combination of the poor leaving ability of the anilinium ion and acyl activation present in the substrate trifluoroacetanilide.
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.
Solvent-freeN-Boc deprotection byex situgeneration of hydrogen chloride gas
De Borggraeve, Wim M.,Gilles, Philippe,Van Mileghem, Seger,Verschueren, Rik H.
supporting information, 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.
