107-12-0Relevant articles and documents
Application of the Water-gas Shift Reaction. III. Reduction of Oxidized Nitrogen Compounds with CO and H2O Catalyzed by (BPh4)2
Okano, Tamon,Fujiwara, Kensuke,Konishi, Hisatoshi,Kiji, Jitsuo
, p. 1975 - 1976 (1982)
The ruthenium(II) complex, 4>(BPh4)2 (cod=1,5-cyclooctadiene, py=pyridine) has been shown to catalyze the reduction of oxidized nitrogen compounds with CO and H2O.In this reaction, primary, secondary, and tertiary nitroalkanes are converted into amides, ketones, and amines, respectively.Nitrosobenzene and picoline N-oxides are also reduciable to amines in good yields.
Preparation of Highly Active Hydrogenation Catalyst by Immobilization of Polymer-Protected Colloidal Rhodium Particles
Hirai, Hidefumi,Ohtaki, Michitaka,Komiyama, Makoto
, p. 149 - 152 (1987)
Colloidal dispersion of rhodium protected by copolymer of mathyl acrylate and N-vinyl-2-pyrrolidone is treated with polyacrylamide gel having amino groups, resulting in immobilization of the rhodium particles onto the gel.The gel-immobilized rhodium particles exhibit 2-22 fold larger catalytic activities than a rhodium carbon catalyst for hydrogenation of olefins at 30 deg C under 1 atm.
Calixarene-Catalyzed Generation of Dichlorocarbene and Its Application to Organic Reactions: The Catalytic Action of Octopus-Type Calixarene
Nomura, Eisaku,Taniguchi, Hisaji,Otsuji, Yoshio
, p. 792 - 799 (1994)
The dichlorocarbene generation reaction from CHCl3 and solid KOH in CH2Cl2 was catalyzed by the p-t-butylcalixarene derivative 1 which bears six 3,6,9-trioxadecyl substituents on the phenolic oxygens.Dichlorocarbene generated by this method reacted efficiently with alkenes and amides to give dichlorocyclopropane derivatives and nitriles, respectively, in high yields.The reaction with alkadiene having isolated double bonds gave mixtures of the mono- and bis-dichlorocarbene adducts, but the monoadduct formation always predominated.The catalytic action of the calixarene and the reactivity features of dichlorocarbene generated by the above procedure are discussed on the basis of kinetic measurements.They are also compared with those of the 18-crown-6-catalyzed reactions.
Study on the conversion of glycerol to nitriles over a Fe 19.2K0.2/γ-Al2O3 catalyst
Zhang, Yuecheng,Ma, Tianqi,Zhao, Jiquan
, p. 92 - 103 (2014)
An Fe19.2K0.2/γ-Al2O3 catalyst for the catalytic amination of glycerol to propionitrile was prepared. Acetonitrile as a major product was obtained over this catalyst from the amination of glycerol. Additionally, propionitrile, ethylene and propylene were also obtained. The parameters influencing the catalyst performance were studied thoroughly, and an optimised process for the amination of glycerol to acetonitrile and propionitrile over the catalyst was obtained. Under the optimised conditions, which were a reaction temperature of 525 °C, an atmospheric pressure with an ammonia/glycerol molar ratio of 8:1 and GHSV of 1338 h-1, the total yield of acetonitrile and propionitrile was 58.4%, and the converted amount of glycerol over one gram of catalyst reached 0.42 g h-1. The catalyst was characterised by XRD, XPS, TEM and IR of the adsorbed pyridine. The characterisation results indicated that the dehydration reaction in the tandem reaction mainly occurred on the Lewis acid sites and revealed that both Fe2O3 and Fe 3O4 are active species for the dehydrogenation of imines to nitriles, but the former is more active than the latter. It also revealed that the catalyst deactivation was due to carbon deposits, the transformation of Fe2O3 to the Fe3O4 phase, as well as agglomeration of the Fe2O3 or Fe3O 4 phase during the catalytic run and regeneration process.
Synergistic Effects of Superbasic Catalysts on the Selective Formation of Acrylonitrile via Oxidative Methylation of Acetonitrile with Methane
Ruckenstein, Eli,Khan, Ashraf Z.
, p. 390 - 401 (1994)
The oxidative methylation of acetonitrile with methane to acrylonitrile occurs more actively and selectivelybialkali promoted CaO catalysts thanany monoalkali promoted system.The most effective catalytic systems are obtained with LiA + CsA, NaA + CsA, or KA + CsA (A = SO42- , OH-, Cl-, CH3COO-, CO32-, or NO3-) supported on CaO, containing total alkali loadings of 10 molpercent with equal molar amounts of both alkalis.At 750 deg C, under atmospheric pressure, at CH4 : O2 : CH3CN : He partial pressure ratios of 5.0 : 1.0 : 1.5 : 6.5, and at a space velocity of 15,000 cm3 g-1 h-1, the highest selectivity to acrylonitrile (70.0 molpercent) and yield (25 percent) are obtained(5 molpercent Na+ + 5 molpercent Cs+)/CaO (prepared from the sulfate precursors).Any bialkali-promoted system containing Rb was less effective, whereas the Li-containing systems, though active initially, gradually lost the activity due to its volatility.The performances of the effective bialkali systems, after an initial increase, remained almost unchanged for a period of 60 h.In contrast, the stability of any monoalkali promoted system with time-on-stream was very low and the maximum initial yield of acrylonitrile was only 11.5 percent under the aforementioned conditions.The synergistic increase in the catalytic performance of the bialkali promoted CaO is reflected in the synergistic increase of the surface basicity (leading to superbasicity) caused by the high enrichment of the surface layer with the alkali ions.The relationship between the catalytic performances and the physicochemical characteristics of the catalysts revealed by XPS, AAS, and basicity measurement is explored.
Synergy in N-Ethylformamide Dehydration by Mixtures of MoO3 and α-Sb2O4
Zhou, B.,Ceckiewicz, S.,Delmon, B.
, p. 5061 - 5067 (1987)
Mixtures of separately prepared MoO3 and α-Sb2O4 show a remarkable synergy in the dehydration of N-ethylformamide to propionitrile when a small amount of oxygen is fed together with the main reagent.The surface acidity of the samples was investigated by TPD of ammonia.ESR and XPS were used for investigating the behavior of the mixtures in reducing and oxidizing conditions.The acidity is attributed mainly to Bronsted sites situated on MoO3.Oxygen is neccessary to maintain these sites.The interpretation is that oxygen is provided, to the surface of MoO3, in the form of spillover oxygen, by α-Sb2O4.Such a mechanism corresponds to what has been called a remote control.
Thermal Decomposition of 5-Methylisoxazole. Experimental and Modeling Study
Lifshitz, Assa,Wohlfeiler, Dror
, p. 7367 - 7375 (1992)
The thermal decomposition of 5-methylisoxazole was studied behind reflected shocks in a pressurized driver single-pulse shock tube over the temperature range 850-1075 K and overall densities of ca. 2.5 * 10-5 mol/cm3.Propionitrile and carbon monoxide are the major decomposition products, followed by ethane, methane, acetonitrile, and hydrogen cyanide.There is no effect of large quantities of toluene (/ ca. 10) on the concentrations of propionitrile and acetonitrile, indicating that no radical chains are involved in their production.It is suggested that the formation of C2H5CN and CO in 5-methylisoxazole involves an N-O bond cleavage in the 1,2-position, a methyl group shift from position 5 to 4, and a rupture of the C(4)-C(5) bond with the removal of carbon monoxide from the ring: 5,m-isox -> C2H5CN + CO (1).In contradiction to findings in isoxazole, this process requires a very large N-O bond stretch which results in a very loose transition state corresponding to a biradical mechanism.The rate constant for this reaction is k1 = 1017.76exp(-70 * 103/RT) s-1 where R is expressed in units of cal/(K mol).The presence of ethane and methane in the postshock mixtures indicates the presence of methyl radicals in the hot phase.It is suggested that the formation of methyl radicals involves the same N-O bond cleavage as in reaction 1 but without the methyl group shift: 5,m-isox -> CH2CN. + CH3CO. (2) followed by CH3CO. -> CH3. + CO (3).This is an endothermic reaction which proceeds at a lower rate than reaction 1 but at a much higher rate than a direct methyl group ejection from the ring.
Studies on V2O5-TiO2 System. Part 1. -TiO2(rutile)-V2O5
Machej, T.,Remy, M.,Ruiz, P.,Delmon, B.
, p. 715 - 722 (1990)
Mechanical mixtures of separately prepared V2O5 and TiO2(rutile) have been used as catalysts in the dehydration of N-ethylformamide (NEF) in the presence of oxygen.Catalytic activity has been measured as a function of the gas hourly space velocity (GHSV),
Intrinsic Barriers in Nucleophilic Displacements. A General Model for Intrinsic Nucleophilicity toward Methyl Centers
Pellerite, Mark J.,Brauman, John I.
, p. 2672 - 2680 (1983)
The applicability of the Marcus rate-equilibrium formalism to the double-minimum potential energy surface for gas-phase SN2 reactions is proposed and used to develop a model for intrinsic nucleophilicity toward methyl centers.The key quantities in this model are the energy barriers to degenerate reactions of the form X(-*)CH3X -> XCH3(*)X(-), in which the reacting species are ion-molecule cluster intermediates.Available experimental and theoretical data corroborate several of the model's predictions.A new structure-nucleophilicity correlation is proposed, involving methyl cation affinities.The model suggests that delocalization effects do not greatly influence nucleophile reactivity.
The effect of solvent on the structure of the transition state for the SN2 reaction between cyanide ion and ethyl chloride in DMSO and THF probed with six different kinetic isotope effects
Fang, Yao-Ren,MacMillar, Susanna,Eriksson, Jonas,Kolodziejska-Huben, Magdalena,Dybala-Defratyka, Agnieszka,Paneth, Piotr,Matsson, Olle,Westaway, Kenneth Charles
, p. 4742 - 4747 (2006)
The secondary α- and β-deuterium, the α-carbon, the nucleophile carbon, the nucleophile nitrogen, and the chlorine leaving group kinetic isotope effects for the SN2 reaction between cyanide ion and ethyl chloride were determined in the very slightly polar solvent THF at 30 °C. A comparison of these KIEs with those reported earlier for the same reaction in the polar solvent DMSO shows that the transition state in THF is only slightly tighter with very slightly shorter NC-Cα and Cα-Cl bonds. This minor change in transition state structure does not account for the different transition structures that were earlier suggested by interpreting the experimental KIEs and the gas-phase calculations, respectively. It therefore seems unlikely that the different transition states suggested by the two methods are due to the lack of appropriate solvent modeling in the theoretical calculations. Previously it was predicted that the transition state of SN2 reactions where the nucleophile and the leaving group have the same charge would be unaffected by a change in solvent. The experimental KIEs support this view.
An XRD, XPS, and EPR study of Li/MgO catalysts: Case of the oxidative methylation of acetonitrile to acrylonitrile with CH4
Bothe-Almquist, Catherine L.,Ettireddy, Reddy P.,Bobst, Albert,Smirniotis, Panagiotis G.
, p. 174 - 184 (2000)
The effects of the Mg and Li precursors and the catalyst surface properties on the catalytic performance in the oxidative methylation of acetonitrile were studied. The performance of the catalysts for the oxidative methylation of acetonitrile to acrylonitrile with CH4 was significantly affected by the Li precursor, where the catalysts prepared with LiCl and LiOH on MgO had the best performance for this reaction. Relatively high BET surface areas had a negative effect on the catalysts' performance by producing less acrylonitrile and more COx. XPS and XRD analyses of Li/MgO-based catalysts showed that the lithium salts used in the catalyst synthesis predominantly formed mixtures with MgO. The Li/Cl atomic ratio was 1:1 in catalysts prepared with LiCl, even after calcination at 650°C for 14 hr in air. The catalysts synthesized with LiCl and LiOH promoted the desired reaction, or equivalently associated with Li+O- species. The catalysts synthesized with LiNO3 showed superior thermal stability, even under severe calcination conditions.
Experimental and theoretical multiple kinetic isotope effects for an SN2 reaction. An attempt to determine transition-state structure and the ability of theoretical methods to predict experimental kinetic isotope effects
Fang, Yao-ren,Gao, Ying,Ryberg, Per,Eriksson, Jonas,Kolodziejska-Huben, Magdalena,Dybala-Defratyka, Agnieszka,Madhavan,Danielsson, Rolf,Paneth, Piotr,Matsson, Olle,Westaway, Kenneth Charles
, p. 2696 - 2709 (2003)
The secondary α-deuterium, the secondary β-deuterium, the chlorine leaving-group, the nucleophile secondary nitrogen, the nucleophile 12C/13C carbon, and the 11C/14C α-carbon kinetic isotope effects (KIEs) and activation parameters have been measured for the SN2 reaction between tetrabutylammonium cyanide and ethyl chloride in DMSO at 30°C. Then, thirty-nine readily available different theoretical methods, both including and excluding solvent, were used to calculate the structure of the transition state, the activation energy, and the kinetic isotope effects for the reaction. A comparison of the experimental and theoretical results by using semiempirical, ab initio, and density functional theory methods has shown that the density functional methods are most successful in calculating the experimental isotope effects. With two exceptions, including solvent in the calculation does not improve the fit with the experimental KIEs. Finally, none of the transition states and force constants obtained from the theoretical methods was able to predict all six of the KIEs found by experiment. Moreover, none of the calculated transition structures, which are all early and loose, agree with the late (product-like) transition-state structure suggested by interpreting the experimental KIEs.
Synthesis of: N -unsubstituted cycloalkylimines containing a 4 to 8-membered ring
Guillemin, Jean-Claude,Nasraoui, Wafa,Gazzeh, Houda
, p. 5647 - 5650 (2019)
Primary cycloalkylimines with a 4 to 8-membered ring were synthesized by dehydrocyanation of the corresponding α-aminonitriles on solid potassium hydroxide via a vacuum gas-solid reaction. Imine-enamine tautomerism has been demonstrated at room temperature for the most kinetically stable derivatives.
Thermolytic synthesis of graphitic boron carbon nitride from an ionic liquid precursor: Mechanism, structure analysis and electronic properties
Fellinger, Tim-Patrick,Su, Dang Sheng,Engenhorst, Markus,Gautam, Devendraprakash,Schloegl, Robert,Antonietti, Markus
, p. 23996 - 24005 (2012)
Recent work has shown the potential of ionic liquids (ILs) as a precursor for porous networks and nitrogen doped carbon materials. The combination of liquid state and negligible vapour pressure represents almost ideal precursor properties and simplifies the processing drastically. Here, we extend this work to get a deeper insight into the solid formation mechanism and to synthesize a mixed boron carbon nitride species by the thermolysis of N,N′- ethylmethylimidazolium tetracyanoborate (EMIM-TCB), a well-known boron- and nitrogen-containing IL. In contrast to other molecule pyrolysis routes boron carbon nitride shows the average composition BC3N and like other IL-derived materials turns out to be distorted graphitic, but thermally and chemically very stable, and possesses favourable electrical properties. The detailed mechanistic investigation using TG-IR, FT-IR, solid-state NMR, Raman, WAXS, EELS, XPS and HRTEM also contributes to the general understanding of IL-based material formation mechanisms. The Royal Society of Chemistry 2012.
Radical Mechanism for the Laser-Induced Explosion of Methyl Isocyanide
Shultz, M. J.,Tricca, Robert E.,Berets, S. L.,Kostas, Christopher,Yam, Loretta M.
, p. 3113 - 3117 (1985)
The laser-induced isomerization of methyl isocyanide has previously been shown to exhibit a marked pressure dependence; large-scale isomerization occurs when threshold conditions have been exceeded.Recent investigations of this large-scale isomerization have shown that the threshold is not due to a thermal mechanism as previously believed.In this work, the characteristics of the threshold are examined and it is shown that the threshold is a result of a radical channel.
Studies on V2O5-TiO2 System. Part 3. -Monolayers of V2O5
Machej, Tadeusz,Ruiz, Patricio,Delmon, Bernard
, p. 731 - 738 (1990)
The catalytic behaviour of anatase- and rutile-vanadium monolayer-like ccatalysts has been studied in the dehydration of N-ethylformamide (NEF) in the presence of oxygen.The catalysts were prepared using two methods: grafting and impregnation.Physicochemi
Infrared Laser-Induced Reaction of Ethyl Isocyanide: Comparison with Methyl Isocyanide
Yam, L. M.,Shultz, M. J.,Rock, Elizabeth J.,Buchau, Susanne
, p. 4632 - 4636 (1988)
Results from the infrared laser-induced reaction of ethyl isocyanide indicate the overall behaviour to be similar to that of methyl isocyanide with some significant differences.Similarities include the following: (1) both exhibit a dramatic dependence of nitrile yield on reactant pressure, including a threshold pressure above which massive isomerization occurs; (2) this threshold pressure is not due to a thermal explosion; (3) both contain a radical channel along with the isomerization channel.Major differences between the methyl isocyanide and ethyl isocyanide reactions are attributable to the nature of the radicals in the particular isocyanide system.
(Ethylene)ethylnickel Cyanide Complex Intermediate in Catalytic Hydrocyanation of Ethylene. Reductive Elimination by an Associative Process
McKinney, Ronald J.,Roe, D. Christopher
, p. 261 - 262 (1985)
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Synthesis of nitriles from acetonitrile and methanol in the presence of oxide catalysts
Lapidus,Tsapkina,Kravtsova,Gorlov
, p. 1476 - 1478 (1997)
The promoting effect of potassium included in Cr/MgO catalysts for the synthesis of nitriles from acetonitrile and methanol was found. The 5% Cr - 0.5% K/MgO catalyst exhibited the highest activity in the synthesis of nitriles.
SELECTIVE REDUCTION OF CONJUGATED DOUBLE BONDS WITH MOLECULAR HYDROGEN AND PALLADIUM(II) COMPLEXED TO FERROCENYLAMINE SULFIDE CATALYSTS
Ali, Hussein M.,Naiini, Ahmad A.,Brubaker, Carl H.
, p. 5489 - 5492 (1991)
Highly catalytic chemo- and regioselectivity have been achieved for the reduction of carbon-carbon double bonds conjugated to different unsaturated functional groups by molecular hydrogen and palladium(II) complexes of ferrocenylamine sulfides.Chemical yields and selectivities were more than 99percent in many cases.
Solid Base-catalysed Rearrangement of Methacrylonitrile to Crotononitrile
Kurokawa, Hideki,Nakamura, Satoru,Ueda, Wataru,Morikawa, Yutaka,Moro-oka, Yoshihiko,Ikawa, Tuneo
, p. 658 - 659 (1989)
MgO and CaO catalysts have shown high activity for the formation of crotonitrile (cis/trans=6/4) in the rearrangement of methacrylonitrile.
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Ferris
, p. 580 (1959)
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Studies on V2O5-TiO2 System. Part 2. -TiO2(anastase)-V2O5
Machej, Tadeusz,Remy, Marc,Ruiz, Patricio,Delmon, Bernard
, p. 723 - 730 (1990)
Mechanical mixtures of separately prepared V2O5, V6O13 and anatase have been used as catalysts in the dehydration of N-ethylformamide (NEF) in the presence of oxygen.Catalytic activity was measured as a function of the gas hourly space velocity (GHSV), th
Reactions of Acetonitrile in a Radiofrequency Discharge
So, Ying-Hung,Bezuk, Steve J.,Miller, Lary L.
, p. 1475 - 1479 (1982)
Acetonitrile was flowed through an inductively coupled radiofrequency (rf) discharge.The products formed under various conditions of power and flow rate were isolated and quantitated by using gas chromatography.The major products were propionitrile, ethane, and hydrogen cyanide.Reaction of mixtures of acetonitrile and cyclohexane gave these three products and cyanocyclohexylmethane, methylcyclohexane, and cyclohexene.All six products can be rationalized by neutral radical reactions.Emission spectroscopy on acetonitrile plasmas showed the expected CN bands from the excited A2? and B2Σ+ states.Analysis of the peak intensities gave a vibrational temperature of ca. 5900K and a rotational temperature of ca. 735K for B2Σ+ state.Lower power, higher pressure, or added ethane diminished the emission intensity but did not change these temperatures.Added argon had no effect up to a mole fraction of argon of 0.8.The absence of cyanoalkanes from plasmas containing CN and alkyl radicals is noted.
Emeleus, H. J.,Wade, K.
, (1960)
Ambient Hydrogenation and Deuteration of Alkenes Using a Nanostructured Ni-Core–Shell Catalyst
Beller, Matthias,Feng, Lu,Gao, Jie,Jackstell, Ralf,Jagadeesh, Rajenahally V.,Liu, Yuefeng,Ma, Rui
supporting information, p. 18591 - 18598 (2021/06/28)
A general protocol for the selective hydrogenation and deuteration of a variety of alkenes is presented. Key to success for these reactions is the use of a specific nickel-graphitic shell-based core–shell-structured catalyst, which is conveniently prepared by impregnation and subsequent calcination of nickel nitrate on carbon at 450 °C under argon. Applying this nanostructured catalyst, both terminal and internal alkenes, which are of industrial and commercial importance, were selectively hydrogenated and deuterated at ambient conditions (room temperature, using 1 bar hydrogen or 1 bar deuterium), giving access to the corresponding alkanes and deuterium-labeled alkanes in good to excellent yields. The synthetic utility and practicability of this Ni-based hydrogenation protocol is demonstrated by gram-scale reactions as well as efficient catalyst recycling experiments.
A method of synthesizing fatty nitrile by the aliphatic aldehyde
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Paragraph 0027; 0028; 0039; 0040, (2019/05/28)
The invention relates to a method of synthesizing fatty nitrile by the aliphatic aldehyde. The method comprises the following steps: the aliphatic aldehyde, ionic liquid regenerating and ionic liquid in the reactor, to join the two toluene, stirring, of the reflux condensation, in the normal pressure, 90 - 120 °C reaction under 0.5 - 2 h, to obtain the product fatty nitrile; wherein said ionic liquid is 1 - sulfobutyl pyridine bisulphate ionic liquid; ion liquid hydroxylamine salt is 1 - sulfobutyl pyridine bisulphate ion liquid hydroxylamine salt. The invention in one reactor to achieve the fat [...] and fat aldoxime dehydration integrated two-step reaction, the process is simple, easy to operate; to ionic liquid as catalyst and a co-solvent, without the addition of metal salt catalyst and corrosive solvent, environment-friendly.