C:Corrosive;
108-91-8Relevant articles and documents
Reaction of Phospholes with Aldimines: A One-Step Synthesis of Chelating, Alpha-C2-Bridged Biphospholes
Hu, Zhengsong,Li, Zongyang,Zhao, Kang,Tian, Rongqiang,Duan, Zheng,Mathey, Fran?ois
, p. 3518 - 3520 (2015)
Phospholes react with aldimines at 170°C in the presence of mild Lewis acids to give C2-bridged biphospholes in good yields. The mechanism includes a series of [1,5] shifts of the P-substituents around the phosphole ring, a P-H + aldimine condensation, and the formation of a transient three-membered ring that dimerizes.
A Selective Electrocatalytic Cleavage of the Benzyloxycarbonyl Group from Peptides
Casadei, M. Antonietta,Pletcher, D.
, p. 1118 - 1119 (1987)
An electrosynthetic procedure for the cleavage of the benzyloxycarbonyl group from protected amino acids and peptides is described.It is based on the use of a high surface area palladium cathode in methanol/acetic acid and gives an excellent selectivity under very mild conditions.
Formal asymmetric biocatalytic reductive amination
Koszelewski, Dominik,Lavandera, Ivan,Clay, Dorina,Guebitz, Georg M.,Rozzell, David,Kroutil, Wolfgang
, p. 9337 - 9340 (2008)
All for one: A combination of three biocatalysts (ω-transaminase, alanine dehydrogenase, and an enzyme such as formate dehydrogenase for cofactor recycling) catalyze a cascade to achieve the asymmetric transformation of a ketone into a primary α-chiral unprotected amine through a formal stereoselective reductive amination (see scheme). Only ammonia and the reducing agent (formate) are consumed during this reaction. (Chemical Equation Presented).
Commercial catalysts screening for liquid phase nitrobenzene hydrogenation
Couto, Clara Sá,Madeira, Luis M.,Nunes, Clemente Pedro,Araújo, Paulo
, p. 152 - 164 (2016)
In this work, a series of commercially available materials was screened for the catalytic hydrogenation of nitrobenzene (NB). The materials revealed different performances, particularly different activities in what concerns the NB conversion, and notably diverse selectivities towards the industrially desired reaction product, aniline (ANL). The catalysts' active phases are based on Pd and Ni (respectively groups I and II), namely 1 wt.% Pd/Al2O3 (catalyst I.1), 0.3 wt.% Pd/Al2O3 (catalyst I.2), 0.3 wt.% Pd/Al2O3 (catalyst I.3), and 50 wt.% NiO/(Al2O3 + SiO2) (catalyst II.1). The fresh and used materials were characterized by several physical-chemical techniques, specifically scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), nitrogen adsorption (with BET surface area determination), X-ray diffraction (XRD), H2 temperature-programmed reduction (TPR), inductively coupled plasma mass spectrometry (ICP-MS) and elemental (CHNS) analysis. It was shown that the catalysts are stable in the conditions studied and no deactivation was found. The characterization results allowed explaining the catalytic behavior of the tested materials. In particular, catalyst I.1 was found to be the less active, probably due to its much lower BET surface area (and larger Pd particle size). On the other hand, catalyst I.2 was the more active, which was well correlated to the smaller average particle size (along with narrower Pd particle size distribution) and smaller pellet size, although the active metal content is low. Finally, it was observed that catalyst II.1 is the most selective towards light by-products (benzene (Bz), cyclohexylamine (CHA), cyclohexanol (CHOL) and cyclohexanone (CHONA)), probably due to its lower pore size dimensions.
Anti-Markovnikov Hydroamination of Alkenes with Aqueous Ammonia by Metal-Loaded Titanium Oxide Photocatalyst
Park, Soyeong,Jeong, Jaeyoung,Fujita, Ken-Ichi,Yamamoto, Akira,Yoshida, Hisao
, p. 12708 - 12714 (2020)
A completely new route was established to synthesize valuable primary amines from alkenes by using aqueous ammonia, that is, a simple photocatalytic hydroamination of alkenes using aqueous ammonia with a metal-loaded TiO2 photocatalyst. Although the photochemical hydroamination prefers to form amines according to the Markovnikov rule, the new photocatalytic hydroamination gives anti-Markovnikov products predominantly. With an Au-loaded TiO2 photocatalyst, the amine yield reached up to 93% and the regioselectivity of anti-Markovnikov products was above 98%. The reaction mechanism was proposed for the new photocatalytic hydroamination.
Poly(propylene sulfide)-borane: Convenient and versatile reagent for organic synthesis
Smith, Keith,Balakit, Asim A.,El-Hiti, Gamal A.
, p. 7834 - 7839 (2012)
Poly(trimethylene sulfide)-borane adduct has been used as an efficient borane reagent in hydroboration reactions to produce various organoboranes, which have then been used without isolation in further reactions that involve single, double and triple migrations of alkyl groups. The presence of the polymer causes no problems, but there are practical advantages associated with its use, including lack of odour and easy recoverability.
Doped ordered mesoporous carbons as novel, selective electrocatalysts for the reduction of nitrobenzene to aniline
Daems, Nick,Risplendi, Francesca,Baert, Kitty,Hubin, Annick,Vankelecom, Ivo F. J.,Cicero, Giancarlo,Pescarmona, Paolo P.
, p. 13397 - 13411 (2018)
Ordered mesoporous carbons (OMCs) doped with nitrogen, phosphorus or boron were synthesised through a two-step nanocasting method and studied as electrocatalysts for the reduction of nitrobenzene to aniline in a half-cell setup. The nature of the dopant played a crucial role in the electrocatalytic performance of the doped OMCs, which was monitored by LSV with a rotating disk electrode setup. The incorporation of boron generated the electrocatalysts with the highest kinetic current density, whereas the incorporation of phosphorus led to the lowest overpotential. Doping with nitrogen led to intermediate behaviour in terms of onset potential and kinetic current density, but provided the highest selectivity towards aniline, thus resulting in the most promising electrocatalyst developed in this study. Density functional theory calculations allowed explaining the observed difference in the onset potentials between the various doped OMCs, and indicated that both graphitic N and pyrdinic N can generate active sites in the N-doped electrocatalyst. A chronoamperometric experiment over N-doped OMC performed at -0.75 V vs. Fc/Fc+ in an acidic environment, resulted in a conversion of 61% with an overall selectivity of 87% to aniline. These are the highest activity and selectivity ever reported for an electrocatalyst for the reduction of nitrobenzene to aniline, making N-doped OMC a promising candidate for the electrochemical cogeneration of this industrially relevant product and electricity in a fuel cell setup.
Selective reductions. Part 60: Chemoselective reduction of organyl azides with dichloroborane-dimethyl sulfide
Salunkhe, Ashok M.,Veeraraghavan Ramachandran,Brown, Herbert C.
, p. 10059 - 10064 (2002)
The rate and stoichiometry of the reduction of an organyl azide with BH3·THF was examined under standardized conditions at room temperature. Borane derivatives, such as dialkyl-, alkoxy-, and haloboranes were also examined for the reduction of azides. This study revealed BHCl2·SMe2 to be the most suitable reagent for the reduction of azides. The chemoselectivity of this reagent was also studied by reducing n-hexyl azide in the presence of representative series of functional groups, including esters, halides, nitriles, and nitro groups. BHCl2·SMe2 reduces azides in the presence of all of the above functional groups as well as olefins. Taking advantage of the differences in reactivity of BHCl2·SMe2 and BH3·THF or BH3·SMe2, it is now possible to reduce selectively an azide in the presence of olefins or to hydroborate an olefin in the presence of azides by a judicious choice of the reagent.
LIQUID PHASE CO-AMMONOLYSIS OF PHENOL AND CYCLOHEXANOL WITH PALLADIUM-ON-CARBON CATALYST
Hamada, Hideaki,Yamamoto, Makoto,Matsuzaki, Takehiko,Wakabayashi, Katsuhiko
, p. 239 - 240 (1980)
In the presence of Pd/C catalyst, phenol and cyclohexanol are aminated simultaneously to aniline and cyclohexylamine by ammonolysis, while conversion of phenol or cyclohexanol alone is very poor.It is suggested that this amination is caused by hydrogen transfer between phenol and cyclohexanol.Ru/C, Rh/C, and Pt/C are ineffective for this co-amination.
Fe/Fe2O3@N-dopped Porous Carbon: A High-Performance Catalyst for Selective Hydrogenation of Nitro Compounds
Yun, Ruirui,Hong, Lirui,Ma, Wanjiao,Jia, Weiguo,Liu, Shoujie,Zheng, Baishu
, p. 724 - 728 (2019)
Herein, we designed and prepared a novel Fe/Fe2O3-based catalyst, in which a remarkable synergistic effect has been revealed between Fe and Fe2O3 encapsulated in N-doping porous carbon. The Fe-based catalysts were fabricated via pyrolysis a mixture of MIL-101(Fe) and melamine. The catalyst exhibits exceptionally high catalytic activity (TOFs up to 8898 h?1 which is about 100 times higher than the similar kinds of catalysts) and chemoselectivity for nitroarene reduction under mild conditions.
