150-46-9Relevant academic research and scientific papers
Application of Mechanochemical Catalysis to the Synthesis of Boric Acid Esters
Molchanov,Goidin,Golovin,Zolotovskaya,Bogdanov,Volodin
, p. 536 - 541 (2002)
The syntheses of triisopropyl borate and other boric acid esters under conditions of mechanochemical activation (MCA) with the use of zeolite catalysts were presented. The proposed method showed short synthesis times, low energy consumption, higher yields of target products, and the absence of byproducts. The mechanism of the catalytic esterification of boric acid under conditions of MCA was described. The conversion was no > 30%. The introduction of zeolites into the reaction zone increased the degree of conversion because of water removal from the reaction medium. Lower conversions of 2-butanol were related to its high viscosity, as a result of which the intensity of MCA was considerably decreased.
Reaction of triethyl phosphite with boron tribromide
Lewkowski, Jaroslaw,Mortier, Jacques,Vaultier, Michel
, p. 707 - 710 (2000)
Reaction of boron tribromide with triethyl phosphite led to the formation of triethyl tribromoborophosphate 1, a complex bearing a P→B bond.
Methyl camouflage in the ten-vertex: Closo -dicarbaborane(10) series. Isolation of closo -1,6-R2C2B8Me8 (R = H and Me) and their monosubstituted analogues
Bakardjiev, Mario,Tok, Oleg L.,R??i?ka, Ale?,R??i?ková, Zdeňka,Holub, Josef,Hnyk, Drahomír,?palt, Zbyněk,Fanfrlík, Jind?ich,?tíbr, Bohumil
, p. 11070 - 11076 (2018)
Reported are procedures leading to the first types of methyl camouflaged dicarbadecaboranes with fewer than eleven vertices. The compounds contain the closo-1,6-C2B8 scaffolding inside the egg-shaped hepta-decamethyl sheath, which im
Low-Temperature Hypergolic Ignition of 1-Octene with Low Ignition Delay Time
Sheng, Haoqiang,Huang, Xiaobin,Chen, Zhijia,Zhao, Zhengchuang,Liu, Hong
, p. 423 - 434 (2021/02/05)
The attainment of the efficient ignition of traditional liquid hydrocarbons of scramjet combustors at low flight Mach numbers is a challenging task. In this study, a novel chemical strategy to improve the reliable ignition and efficient combustion of hydrocarbon fuels was proposed. A directional hydroboration reaction was used to convert hydrocarbon fuel into highly active alkylborane, thereby leading to changes in the combustion reaction pathway of hydrocarbon fuel. A directional reaction to achieve the hypergolic ignition of 1-octene was designed and developed by using Gaussian simulation. Borane dimethyl sulfide (BDMS), a high-energy additive, was allowed to react spontaneously with 1-octene to achieve the hypergolic ignition of liquid hydrocarbon fuel at -15 °C. Compared with the ignition delay time of pure 1-octene (565 °C), the ignition delay time of 1-octene/BDMS (9:1.2) decreased by 3850% at 50 °C. Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry confirmed the directional reaction of the hypergolic ignition reaction pathway of 1-octene and BDMS. Moreover, optical measurements showed the development trend of hydroxyl radicals (OH·) in the lower temperature hypergolic ignition and combustion of 1-octene. Finally, this study indicates that the enhancement of the low-temperature ignition performance of 1-octene by hydroboration in the presence of BDMS is feasible and promising for jet propellant design with tremendous future applications.
Carboranes as Aryl Mimetics in Catalysis: A Highly Active Zwitterionic NHC-Precatalyst
Selg, Christoph,Neumann, Wilma,L?nnecke, Peter,Hey-Hawkins, Evamarie,Zeitler, Kirsten
supporting information, p. 7932 - 7937 (2017/06/19)
Modern catalysis takes advantage of aryl-based interactions to tune and control reactions. In the design of N-heterocyclic-carbene catalysts, both the electronic and steric nature of the nitrogen substituents play a crucial role. Although hydrocarbon-based systems and especially aryl residues have contributed considerably to overcome multifaceted catalytic challenges, the unique properties of carborane moieties, including delocalized charge, potential planar chirality, and well-known thermodynamic stability, offer unprecedented opportunities to develop new catalysts while being employed as aryl mimetics. We report a straightforward synthetic route to a novel zwitterionic triazolium-based N-heterocyclic carbene (NHC) precatalyst bearing a 7,8-dicarba-nido-undecaboranyl substituent. The catalyst's excellent activity and its broad applicability are demonstrated in a wide range of organocatalytic transformations. Comparison of the performance with known N-aryl NHC catalysts offers preliminary insights into the stereoelectronic nature of this nido-carboranyl substituent.
Rehydrogenation of aminoboranes to amine-boranes using H2O: Reaction scope and mechanism
Leitao, Erin M.,Manners, Ian
, p. 2199 - 2205 (2015/05/13)
Water has been successfully employed as a reagent with which to rehydrogenate aminoboranes (e.g., iPr2N=BH2, 2,2,6,6-Me4C5H6N=BH2, and also transient Me2N=BH2 derived from 1/2[Me2N-BH2]2) to amine-boranes (e.g., iPr2NH·BH3, 2,2,6,6-Me4C5H6NH·BH3, Me2NH·BH3) in approximately 30 yield. The conversion to amine-boranes from the corresponding aminoboranes using this method represents an example of a metal-free, single-step route for the hydrogenation of the B=N bond. Deuterium labeling studies indicated that the protic hydrogen (N-H) on the rehydrogenated amine-borane was derived from H2O, whereas the third hydridic hydrogen (B-H) on the amine-borane was generated from the formation of a postulated hydride-bridged intermediate H2B(μ-H)(μ-NR2)B(OH)H (R2 = Me2, iPr2, 2,2,6,6-Me4C5H6), which requires a second equivalent of the starting aminoborane, thus explaining the low yield. Formation of insoluble borates (BxOyHz) provides a driving force for the reaction. Significantly, the yield can be increased by adding a sacrificial source of BH3 (e.g., to ca. 53% for BH3·THF) or by adding a separate source of H- (e.g., to ca. 95% for LiBH4) to complement the H+ (from H2O) in a more atom-efficient reaction.
Gold(I) complexes of tetrathiaheterohelicene phosphanes
Cauteruccio, Silvia,Loos, Annette,Bossi, Alberto,Blanco Jaimes, Maria Camila,Dova, Davide,Rominger, Frank,Prager, Stefan,Dreuw, Andreas,Licandro, Emanuela,Hashmi, A. Stephen K.
, p. 7995 - 8004 (2013/08/23)
New tetrathia[7]helicene-based (7-TH-based) gold(I) complexes 6 and 7 have been readily prepared by reaction of the respective phosphine ligands 2 and 3 with Au(tht)Cl in a 1:1 and 1:2 molar ratio, respectively. These complexes have been fully characterized by analytical and spectroscopic techniques as well as quantum chemical calculations. The molecular structure of dinuclear complex 7 has been determined by single-crystal X-ray diffraction, showing a gold-gold interaction of 3.1825(3) A and a significant contraction of the 7-TH total dihedral angle. Au(I) complex 7 displays luminescence emission at room and low temperature in diluted solution and in the solid state. Quantum chemical calculations show that the luminescence emission at room temperature is primarily due to slightly perturbed fluorescence emission from purely ππ* excited states of the conjugated helicene scaffold. At 77 K phosphorescence emission is displayed as well. Preliminary studies on the use of 6 and 7 as catalysts in typical Au(I)-catalyzed cycloisomerizations have demonstrated the reactivity of these systems in the intramolecular allene hydroarylations and the hydroxycarboxylation of allene-carboxylates.
Pronounced solvent effect on the hydrostannylation of propargylic alcohol derivatives with nBu3SnH/Et3B at room temperature
Oderinde, Martins S.,Organ, Michael G.
supporting information, p. 2615 - 2618 (2013/03/14)
The solvent is key: A general protocol is described for the hydrostannylation of propargyl alcohol derivatives at room temperature using Et3B/O2 as the promoter (see scheme). Rate and mechanistic studies point to a different autoxidation product of Et3B in THF than is observed in benzene, the typical solvent. Copyright
A mild and efficient rhenium-catalyzed transfer hydrogenation of terminal olefins using alcoholysis of amine-borane adducts as a reducing system
Dong, Hailin,Berke, Heinz
experimental part, p. 1803 - 1808 (2011/06/19)
[ReBr2(NO)(CH3CN)(PTA)2] (PTA = 1, 3, 5-triaza-7-phosphaadamantane) catalyzes the alcoholysis of ammonia-borane and amine-boranes and the catalytic transfer hydrogenations of various terminal olefins. Excellent yields were achieved at 70 °C in isopropanol using tBuOK as a co-catalyst affording TOF values up to 396 h-1.
Triorganyl- and diorganyloxozirconium hydridoborates - Synthesis and structures
Knizek, Joerg,Noeth, Heinrich,Schmidt-Amelunxen, Martin
, p. 5548 - 5557 (2012/02/04)
The reactions of Zr(OBu)4 and Zr(OEt)4 with H 3B·THF in THF led to HB(OR)2 and B(OR)3, but no zirconium tetrahydroborate [(RO)4-nZr(BH4) n] could be isolated. On the contrary, the reactions of [tBu 3CO]4-nZrCln and [tBu3SiO] 4-nZrCln with LiBH4 generated the tetrahydroborates [(RO)3Zr(BH4)] and [(RO) 2Zr(BH4)2]. These can be used to produce by hydroborate exchange dihydridodiorganyl borates [(RO)4-nZr(H 2BC8H14)n] and byproducts. The structures of the new zirconium hydridoborates have been determined by X-ray crystallography. Compound [(tBu3CO)3Zr(H 2BC8H14)] shows site-disordered dihydroborate units with agostic Zr-H-C interactions, while [(tBu3SiO) 2Zr(H2BC8H14)2] is quite symmetric (C2/c). The corresponding tetrahydridoborates possess in most cases μ31-bonded ZrH3BH groups. Compounds of the type [(RO)4-nZr(BH4)n] were obtained from the reaction of(RO)4Zr (R = Bu, Et) with H 3B·THF or that of (RO)4-nZrCln(n = 1, 2; R = tBu3C, tBu3Si) with LiBH4. Boryl group exchange with H2BC8H14- leads to (RO)4Zr(H2BC8H14)n with agostic Zr-H-B bonding when n = 1, whereas a symmetric ZrH2B compound results when n = 2. Copyright
