- Probing the synergistic effect of Mo on Ni-based catalyst in the hydrogenation of dicyclopentadiene
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Mo promoted Ni/γ-Al2O3 catalysts were synthesized by an incipient wetness co-impregnation method. The micro-structure, surface composition and adsorption characteristics of these catalysts were investigated by N2 adsorption-desorption isotherms, XRD, HRTEM, XPS, TPR and dicyclopentadiene-TPD. The hydrogenation of dicyclopentadiene (DCPD) to endo-tetrahydrodicyclopentadiene (endo-THDCPD) was selected to evaluate the catalytic performance. The results showed Mo species improved dispersity of nickel oxide on the support surface and inhibit formation of spinel NiAl2O4. The nickel oxide could be reduced to Ni nanoparticles at relatively lower temperature because of its excellent dispersity and weakened interaction with the support. Meanwhile, the aggregation of metallic Ni on catalysts were markedly inhibited with the increasing of Mo content. Mo species also changed the adsorption mode of DCPD on Ni-based catalysts, and hence improved DCPD adsorption strength and capacity on catalysts and further changed hydrogenation mechanism of DCPD. The catalytic properties of NiMoX/γ-Al2O3 catalysts showed that the hydrogenation activity was increased by adding Mo to Ni-based catalyst within limits. When the ratio of Mo to Ni was 0.2, the NiMo0.2/γ-Al2O3 catalyst displayed the highest activity (TOF = 134.2 h?1) and the best selectivity (99.7%). Compared with Ni/γ-Al2O3 catalyst, the hydrogenation time reduced from 6 h to 3 h and the amount of by-product C5 fraction significantly decreased from 2.4% to 0.3%.
- Fang, Zhuqing,Shi, Daxin,Lin, Na,Li, Airu,Wu, Qin,Wang, Qiqi,Zhao, Yun,Feng, Caihong,Jiao, Qingze,Li, Hansheng
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- A NEW APPROACH TO THE BICYCLO ( 5.2.1 ) DECANE SYSTEM.
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A simple route to the bicyclo ( 5.2.1 ) decane system by oxidation of trimethylenenorbornane is demonstrated.
- Klimko, Yu. E.,Isaev, S. D.,Yurchenko, A. G.
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- Features of dicyclopentene formation during hydrogenation of dicyclopentadiene
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General trends and specific features of the reaction of dicyclopentadiene (tricyclo[5.2.1.02.6]decadiene-3,8) hydrogenation to dicyclopentene (tricycle[5.2.1.02.6]decene-3) with hydrogen in the liquid phase under mild conditions at atmospheric pressure over a finely divided 1% Pd/C catalyst have been studied. The kinetic parameters that characterize the effect of the solvent nature, catalyst concentration, and temperature on the rate of hydrogen uptake in the hydrogenation process have been determined. To substantiate the conclusion of the sequence of saturation of the dicyclopentadiene double bonds in terms of the mechanism of heterogeneous catalysis, their reactivity has been compared. It has been shown that in the presence of a number of functionalized aromatic compounds as a stabilizing additive, the yield of desired dicyclopentene increases to 98.5-99 mol % with the complete conversion of dicyclopentadiene. The structure of dicyclopentadiene and its hydrogenation product dicyclopentene has been confirmed using spectroscopic methods.
- Vereshchagina,Antonova,Il'In,Chirkova, Zh. V.
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- Single-step catalytic liquid-phase hydroconversion of DCPD into high energy density fuel exo-THDCPD
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Hydroconversion of dicyclopentadiene (DCPD) into high energy density jet propellant JP-10 has been successfully achieved with a greener single-step route over supported gold catalyst. The physicochemical properties of the catalysts were studied with XRD, SEM, TEM, N2-adsorption, NH3-TPD. The influence of reaction conditions like temperature, pressure, time etc. were studied in detail. The studies reveal that pressure and temperature play crucial roles in the reaction. Moderate acid sites in the catalysts are chiefly involved in isomerization and gold catalyzes hydrogenation of the intermediates. Analysis of the product stream at different intervals indicates a dissociation-recombination mechanism for the reaction. Reusability of the catalyst was tested by conducting five runs with the same catalyst. Even after the fifth run, the catalyst retains relatively high conversion and selectivity to exo-tetrahydrodicyclopentadiene (exo-THDCPD).
- Sibi,Singh, Bhawan,Kumar,Pendem,Sinha
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- Low-temperature heat capacity and thermodynamic properties of endo-Tricyclo[5.2.1.02,6]decane
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Endo-Tricyclo[5.2.1.02,6]decane (CAS 6004-38-2) is an important intermediate compound for synthesizing diamantane. The lack of data on the thermodynamic properties of the compound limits its development and application. In this study, endo-Tricyclo[5.2.1.02,6]decane was synthesized and the low temperature heat capacities were measured with a high-precision adiabatic calorimeter in the temperature range from (80 to 360) K. Two phase transitions were observed: the solid-solid phase transition in the temperature range from (198.79 to 210.27) K, with peak temperature 204.33 K; the solid-liquid phase transition in the temperature range from 333.76 K to 350.97 K, with peak temperature 345.28 K. The molar enthalpy increments, ΔH m, and entropy increments, ΔSm, of these phase transitions are ΔHm, = 2.57 kJ · mol-1 and ΔSm = 12.57 J · K-1 · mol -1 for the solid-solid phase transition at 204.33 K, and, ΔfusHm = 3.07 kJ · mol-1 and ΔfusSm = 8.89 J · K-1 · mol-1 for the solid-liquid phase transition at 345.28 K. The thermal stability of the compound was investigated by thermogravimetric analysis. TG result shows that endo-Tricyclo[5.2.1.02,6]decane starts to sublime at 300 K and completely changes into vapor when the temperature reaches 423 K, reaching the maximal rate of weight loss at 408 K.
- Kong, Li-Guo,Tan, Zhi-Cheng,Xu, Jie,Meng, Shuang-He,Bao, Xin-He
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- Isomerization of endo-tetrahydrodicyclopentadiene over clay-supported chloroaluminate ionic liquid catalysts
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Various halide salts with different alkyl lengths were allowed to intercalate into the layer structure of sodium montmorillonite clay through an ion exchange reaction. Intercalation of 1-hexadecyl-3-methylimidazolium chloride, hexadecyltrimethylammonium bromide, dihexadecyldimethylammonium bromide, and tributylhexadecylphosphonium bromide could expand the spacing of the silicate layers from 12 to 37-41 ? (measured by X-ray diffraction). The modified clays were pretreated with the pyridine hydrochloride/AlCl3 mixture and used for suitably supporting a chloroaluminate ionic liquid catalyst for the isomerization of endo-tetrahydrodicyclopentadiene into the corresponding exo-isomer. Nearly quantitative conversion to the desired product and nearly quantitative selectivity were observed for the newly developed clay-supported ionic liquid catalysts, which were proven to be recyclable.
- Huang, Ming-Yu,Wu, Jung-Chung,Shieu, Fuh-Sheng,Lin, Jiang-Jen
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- Hydrogenation of Dicyclopentadiene in the Presence of a Nickel Catalyst Supported onto a Cation Exchanger in a Flow-Type Reactor
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The process of dicyclopentadiene hydrogenation in the gas–liquid–solid catalyst system with a catalyst of nickel nanoparticles supported onto a Purolite CT-175 cation exchange resin was studied. The surface structure of the catalyst and the kinetics of the dicyclopentadiene hydrogenation process were examined. Optimum conditions were found for the production of endo-tetrahydrodicyclopentadiene and the simultaneous production of endo-tetrahydrodicyclopentadiene and 5,6-dihydrodicyclopentadiene at atmospheric pressure.
- Popov, Yu. V.,Mokhov,Nebykov,Latyshova,Shcherbakova,Panov
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- Nickel nanocatalyst supported single-step hydroconversion of dicyclopentadiene (DCPD) into high energy-density fuel, exo-tetrahydrodicyclopentadiene (Exo-THDCPD)
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There are several chemical methods for the synthesis of high energy-density fuel, exo-tetrahydrodicyclopentadiene (exo-THDCPD), however, still there is a challenge to synthesize exo-THDCPD conveniently. In present work, the exo-THDCPD from dicyclopentadiene (DCPD) has successfully synthesized through simplest and greener single step hydroconversion reaction over mesoporous supported nickel nanocatalyst (Ni/MCM-41). The reaction performed in autoclave under a hydrogen pressure ranging from 300–400 (Psi), temperature range 130–150° C and progress has been dissociation-recombination sure structural and monitored nanocatalyst analysis by of gas exo-THDCPD IP: have chromatography 203.56.241.128 Copyright: of been DCPD. experimentally is Delivered carried The American which major On: out reveals Fri, by by examined reaction Scientific Ingenta 1 12 H that NMR Jul parameters for the 2019 Publishers and the reaction FTIR 03:16:04 yield such techniques (85%) mechanism as of temperature, the and goes product. the through physic- pres-The ochemical properties have also been evaluated. Good quality nanocatalyst Ni/MCM-41 has been synthesized by impregnation incipient wetness method and characterized by XRD, EDAX, TEM, and BET techniques. The nanocatalyst is highly reactive due to its mesoporous structure having appropriate size and shape which gives free diffusion of the molecules. Repeatability of the nanocatalyst shows good reactivity up to the four runs.
- Khan, Nizamuddin,Abhyankar,Nandi, Tandra,Eswara Prasad
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- 19. 1,7-Trimethylenenorborane. A Novel Member of the 'Adamantaneland'
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A synthesis of the novel C10H16 hydrocarbon 1,7-trimethylenenorborane (13), one of the 19 members of the adamantane family, is described.
- Jaggi, Franz Joseph,Ganter, Camille
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- Synthesis of adamantane by ionic liquid-promoted isomerization of tricyclo[5.2.1.02,6]decane and H2SO4-mediated hydroisomerization of pentacyclo[4.4.0.02,4.03,7.08,10]decane
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Adamantane was synthesized by skeletal isomerization of endo- and exo-tricyclo[5.2.1.02,6]-decanes in the presence of ionic liquid [Et3NH]+[Al2Cl7]?—CuSO4. A new method to synthesize adamantane in 75% yield by H2SO4-mediated hydroisomerization of its new precursor, pentacyclo[4.4.0.02,4.03,7.08,10]decane, was developed.
- Aminov,Ramazanov,Khusnutdinov
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p. 102 - 106
(2022/02/17)
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- Preparation method of adamantanone
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The invention discloses a preparation method of adamantanone, and relates to the technical field of adamantanone synthesis. The problems that the reaction time is long and the operation process is tedious are solved. The preparation method specifically comprises the following steps: putting raw materials including adamantane, sulfuric acid and trifluoroacetic acid into a batching kettle, and stirring and mixing at 30 DEG C; raising the temperature to 50 DEG C, and introducing nitrogen into the batching kettle; pressing the mixed materials into a reaction tube, and performing standing for 1 minute; pouring the reaction solution on 500g of ice, adding a NaOH aqueous solution which is 7 times the weight of adamantane during cooling, and adjusting the pH value to 9; and extracting by using methylbenzene of which the weight is 3 times that of adamantane. The raw materials are mixed and then heated, nitrogen is introduced, then an oxidation reaction occurs, the retention time and temperatureof reaction liquid in a reaction tube are controlled in the leading-out period, the reaction liquid is extracted through methylbenzene and the NaOH aqueous solution, the extraction liquid is subjected to reduced pressure distillation concentration, cooling, separation and drying treatment, the final product is obtained, the operation process is relatively simple, the reaction is controllable, andthe time is short.
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Paragraph 0033; 0043; 0052; 0062; 0070; 0080; 0088; 0098;
(2021/04/03)
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- Application of hierarchical pore molecular sieve in preparation process of cyclopentadiene and JP-10 aviation fuel
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The invention relates to an application of a hierarchical pore molecular sieve in a the preparation process of cyclopentadiene and JP-10 aviation fuel. The hierarchical pore molecular sieve is one or two or more of an H-ZSM-5 molecular sieve, an H-beta molecular sieve, an H-Y molecular sieve, an H-USY molecular sieve, a La-Y molecular sieve and an H-MOR molecular sieve with a hierarchical pore structure, a sulfonated SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Ti-SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Zr-MCM-41 molecular sieve and a sulfonated Zr-SBA-15 molecular sieve; and the hierarchical pore structure comprises micropores and mesopores. The catalyst and the raw materials used in the method are cheap and easy to obtain, the preparation process is simple, and the hierarchical pore molecular sieve has high activity and selectivity for rearrangement reaction of furfuryl alcohol, hydrogenation reaction of hydroxyl cyclopentenone and dehydration reaction. The invention provides a cheap and efficient synthesis method for synthesizing the JP-10 aviation fuel from a lignocellulose-based platform compound furfuryl alcohol.
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Paragraph 0023; 0144-0154
(2021/07/01)
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- Dendrimer-Encapsulated Pd Nanoparticles, Immobilized in Silica Pores, as Catalysts for Selective Hydrogenation of Unsaturated Compounds
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Heterogeneous Pd-containing nanocatalysts, based on poly (propylene imine) dendrimers immobilized in silica pores and networks, obtained by co-hydrolysis in situ, have been synthesized and examined in the hydrogenation of various unsaturated compounds. The catalyst activity and selectivity were found to strongly depend on the carrier structure as well as on the substrate electron and geometric features. Thus, mesoporous catalyst, synthesized in presence of both polymeric template and tetraethoxysilane, revealed the maximum activity in the hydrogenation of various styrenes, including bulky and rigid stilbene and its isomers, reaching TOF values of about 230000 h?1. Other mesoporous catalyst, synthesized in the presence of polymeric template, but without addition of Si(OEt)4, provided the trans-cyclooctene formation with the selectivity of 90–95 %, appearing as similar to homogeneous dendrimer-based catalysts. Microporous catalyst, obtained only on the presence of Si(OEt)4, while dendrimer molecules acting as both anchored ligands and template, demonstrated the maximum activity in the hydrogenation of terminal linear alkynes and conjugated dienes, reaching TOF values up to 400000 h?1. Herein the total selectivity on alkene in the case of terminal alkynes and conjugated dienes reached 95–99 % even at hydrogen pressure of 30 atm. The catalysts synthesized can be easily isolated from reaction products and recycled without significant loss of activity.
- Karakanov, Edward A.,Zolotukhina, Anna V.,Ivanov, Andrey O.,Maximov, Anton L.
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p. 358 - 381
(2019/04/04)
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- Making JP-10 Superfuel Affordable with a Lignocellulosic Platform Compound
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The synthesis of renewable jet fuel from lignocellulosic platform compounds has drawn a lot of attention in recent years. So far, most work has concentrated on the production of conventional jet fuels. JP-10 is an advanced jet fuel currently obtained from fossil energy. Due to its excellent properties, JP-10 has been widely used in military aircraft. However, the high price and low availability limit its application in civil aviation. Here, we report a new strategy for the synthesis of bio-JP-10 fuel from furfuryl alcohol that is produced on an industrial scale from agricultural and forestry residues. Under the optimized conditions, bio-JP-10 fuel was produced with high overall carbon yields (≈65 %). A preliminary economic analysis indicates that the price of bio-JP-10 fuel can be greatly decreased from ≈7091 US$/ton (by fossil route) to less than 5600 US$/ton using our new strategy. This work makes the practical application of bio-JP-10 fuel forseeable.
- Li, Guangyi,Hou, Baolin,Wang, Aiqin,Xin, Xuliang,Cong, Yu,Wang, Xiaodong,Li, Ning,Zhang, Tao
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p. 12154 - 12158
(2019/08/12)
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- Colloid and Nanosized Catalysts in Organic Synthesis: XXII. Hydrogenation of Cycloolefins Catalyzed by Immobilized Transition Metals Nanoparticles in a Three-Phase System
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The processes of unsaturated cyclic hydrocarbons hydrogenation in a three-phase gas-liquid-solid catalyst system in the presence of nanostructured nickel, cobalt, or iron catalysts in a flow reactor at 130°C and atmospheric pressure have studied. RX3Extra activated carbon, γ-Al2O3, NaX zeolite, and Purolite CT-175 cation-exchange resin have been used as supports; NaBH4 and NH2NH2·H2O were used as reducing agents. The catalytic activity of supported nanoparticles and their selectivity with respect to the product of exhaustive hydrogenation have been investigated.
- Nebykov,Popov, Yu. V.,Mokhov,Latyshova,Shcherbakova,Nemtseva,Shishkin
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p. 1985 - 1989
(2019/11/29)
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- Method for preparing JP-10 aircraft fuel from furfuryl alcohol
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The invention relates to a method for preparing JP-10 aircraft fuel from furfuryl alcohol. The method for preparing the JP-10 aircraft fuel from furfuryl alcohol comprises the following four reactions: reaction I, in the presence of base catalyst or in the absence of a catalyst, preparing hydroxyl cyclopentenone from a furfuryl alcohol solution through a rearrangement reaction; reaction II, performing a D-A reaction on the hydroxyl cyclopentenone and cyclopentadiene so as to generate a C10 oxygen-containing compound; reaction III, performing hydrodeoxygenation on the C10 oxygen-containing compound generated in the former step so as to obtainendo-tetrahydrodicyclotadiene; and reaction IV, isomerizing the endo-tetrahydrodicyclotadiene, thereby obtaining exo-tetrahydrodicyclopentadiene, wherein theexo-tetrahydrodicyclopentadiene can be directly used as the JP-10 aircraft fuel. The catalyst and the raw materials used in the method are cheap and easy to obtain and have relatively high activity and selectivity for rearrangement reactions of furfuryl alcohol, D-A reactions of hydroxyl cyclopentenone and hydrodeoxygenation. The invention provides a cheap and efficient synthesis method forsynthesizing JP-10 aircraft fuel from a lignocelluloses based platform compound, namely tfurfuryl alcohol.
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- Method for preparing JP-10 aviation fuel from furfuryl alcohol
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The invention relates to a method for preparing JP-10 aviation fuel from furfuryl alcohol. The method for preparing JP-10 aviation fuel by taking the furfuryl alcohol as a raw material is totally divided into six reactions as follows: a first reaction of carrying out a rearrangement reaction on a furfuryl alcohol solution in the presence of a base catalyst or under the condition that any catalystis not added to prepare hydroxy cyclopentenone; a second reaction of reacting the hydroxy cyclopentenone and hydrogen under catalysis of a hydrogenation catalyst so as to prepare 1,3-cyclopendiol; a third reaction of dehydrating the 1,3-cyclopendiol to prepare cyclopentadiene; a fourth reaction of carrying out a D-A reaction on the cyclopentadiene to produce dicyclopentadiene; a fifth reaction ofhydrogenating the dicyclopentadiene to produce endo-tetrahydrodicyclotadiene; and a sixth reaction of performing isomerization on the endo-tetrahydrodicyclotadiene to produce hanging type tetrahydrodicyclopentadiene, wherein the prepared hanging type tetrahydrodicyclopentadiene can directly serve as the JP-10 aviation fuel. The invention provides a cheap high-efficiency synthetic method for synthesizing the JP-10 aviation fuel from a lignocelluloses-based platform chemical compound, namely furfuryl alcohol.
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Paragraph 0151; 0152; 0154; 0155; 0160
(2018/06/16)
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- Colloid and Nanosized Catalysts in Organic Synthesis: XIX.1 Influence of the Support Nature on Hydrogenation Catalysis of Cyclic Olefins by Nickel Nanoparticles
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Gas-phase hydrogenation of cycloalkenes in the presence of nickel nanoparticles supported on Ceokar-2, BAU-A activated carbon, alumina, and NaX zeolite proceeds at 140–240°C and atmospheric pressure of hydrogen. The conversion and selectivity depend on the type of support and on the hydrogen excess.
- Popov, Yu. V.,Mokhov,Nebykov,Shcherbakova,Dontsova
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- Selective Catalytic Hydrogenation of Alicyclic Dienes with Hydrogen in a Liquid Phase
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Abstract: The hydrogenation behavior of a number of alicyclic dienes (5-vinyl-2-norbornene (5-vinyl-bicyclo[2.2.1]heptene-2), dicyclopentadiene (tricyclo[5.2.1.02,6]decadiene-3,8), and cis,cis-1,5-cyclooctadiene) to the corresponding cycloalkenes in the presence of a finely divided palladium catalyst suspended in the liquid phase has been studied. The reactivities of the double bonds of these dienes have been compared. The conversion of 5-vinyl-2-norbornene and selectivity of its hydrogenation to 2-vinylnorbornane depending on the reaction conditions have been evaluated. Conditions for the selective production of desired 2-vinylnorbornane are proposed for the further implementation of this process in practice.
- Bermeshev,Antonova,Shangareev,Danilova,Pozharskaya
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p. 869 - 875
(2018/10/15)
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- Method for preparing JP-10 aviation fuel from furfuryl alcohol
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The invention relates to a method for preparing JP-10 aviation fuel from furfuryl alcohol. The method for preparing the JP-10 aviation fuel by adopting the furfuryl alcohol as a raw material comprises the following five steps: step I, enabling a furfuryl alcohol solution to have a rearrangement reaction to prepare hydroxylcyclopentenone under the condition of an alkaline catalyst or no catalyst; step II, enabling the hydroxylcyclopentenone to react with hydrogen under the catalysis of a hydrogenation catalyst to prepare 1,3-cyclopentanediol; step III, preparing cyclopentadiene or dicyclopentadiene by dehydrating the 1,3-cyclopentanediol; step IV, enabling the cyclopentadiene and the dicyclopentadiene to have an isomerization reaction to generate hanging dicyclopentadiene; and step V, hydrogenating the hanging dicyclopentadiene to generate hanging tetrahydro-dicyclopentadiene, and then rectifying and purifying to obtain the JP-10 aviation fuel. Raw materials used in the method are cheap and easy to obtain, the preparation process is simple, and the activity and selectivity for the rearrangement reaction of the furfuryl alcohol, the hydrogenation reaction of the hydrocyclopentenone and the dehydration reaction is relatively high. The invention provides a synthetic method with low cost and high efficiency for synthesizing the cyclopentadiene or the dicyclopentadiene from lignocelluloses-based platform compound and furfuryl alcohol.
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Paragraph 0118; 0119; 0120; 0121; 0122; 0123-0153
(2017/07/21)
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- Saturation kinetics and relative reactivity of the double bonds of alicyclic dienes in their hydrogenation
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The kinetics of the liquid-phase hydrogenation of cyclodienes with various structures (endo-tricyclo[ 5.2.1.02,6]decadiene-3,8 and cis,cis-1,5-cyclooctadiene) by hydrogen over a finely dispersed 1%Pd/C catalyst at atmospheric pressure has been studied. The catalyst provides the possibility for successive saturation of the double bonds of the dienes. The reactivities of the cyclodienes determined by their electron-donating properties have been compared. The solvent nature is the determining factor in the ratio of hydrogen absorption rates in the case of successive saturation of the double bonds of the hydrocarbons. The hydrogenation kinetics of cyclic dienes, including dicyclopentadiene, can be modeled using the Langmuir–Hinshelwood equation when the process is carried out in a perfectly mixed flow reactor.
- Vereshchagina,Antonova,Kopushkina, G. Yu.,Abramov
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p. 255 - 261
(2017/07/25)
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- Colloidal and nanosized catalysts in organic synthesis: XV. Gas-phase hydrogenation of alkenes catalyzed by supported nickel nanoparticles
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Gas-phase hydrogenation of alkenes and their derivatives, catalyzed by nickel nanoparticles supported on zeolite or silica gel support occurs at 150–250°С and an atmospheric hydrogen pressure and results in a high conversion. The selectivity of the hydrogenation depends on the amount of hydrogen: at a low diene (triene)–hydrogen ratio, selective hydrogenation of one multiple bond in the substrate is possible.
- Popov, Yu. V.,Mokhov,Nebykov,Latyshova,Panov,Dontsova,Shirkhanyan,Shcherbakova
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p. 2589 - 2593
(2017/03/22)
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- Hydrogenation of alkenes over nickel nanoparticles under atmospheric pressure of hydrogen
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Nickel nanoparticles have been shown to be an accessible catalyst which allows hydrogenation of unsaturated compounds to be accomplished under atmospheric pressure of hydrogen at relatively low temperatures. Linear and cyclic alkenes, styrene and norbornene derivatives, as well as pinenes and camphene have been smoothly hydrogenated under these conditions. In some cases, selective hydrogenation of unsaturated carbon–carbon bond is possible with the other functional group remaining intact.
- Mokhov,Popov, Yu. V.,Nebykov
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p. 319 - 323
(2016/06/06)
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- DCPD hydrogenation catalyst used for slowing down the hydrogenation, the deactivation rate of the raw material processing method
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The invention provides a treatment method of a hydrogenation raw material for retarding the inactivation rate of a DCPD (dicyclopentadiene) hydrogenation catalyst. The treatment method is characterized in that a polymerization inhibitor in the hydrogenation raw material is removed by pretreatment such as reduced pressure distillation, alkali washing or adsorption and the like of the hydrogenation raw material so as to retard the inactivation rate of the DCPD hydrogenation catalyst. No matter in batch-type hydrogenation reaction or in fixed-bed continuous reaction, the raw material treated by the method can be used for obviously retarding the inactivation rate of the catalyst.
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Paragraph 0018; 0019
(2017/03/21)
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- What Is the True Structure of D609, a Widely Used Lipid Related Enzyme Inhibitor?
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(Chemical Equation Presented) D609 (1) has been used as a lipid-related enzyme inhibitor during the past three decades. Although it has eight possible stereoisomers, no systematic research considering its chirality has been performed. In this paper, eight possible chiral alcohols as direct precursors of D609 were synthesized, and their stereochemistries were elucidated by a vibrational circular dichroism (VCD) technique. Phosphatidylcholine-specific phospholipase C and sphingomyelin synthase inhibition assays of these isomers showed considerable differences in their activities.
- Kato, Mikako,Hammam, Mostafa A. S.,Taniguchi, Tohru,Suga, Yoshiko,Monde, Kenji
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supporting information
p. 768 - 771
(2016/03/01)
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- Oxygen-Deficient Tungsten Oxide as Versatile and Efficient Hydrogenation Catalyst
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Heterogeneous hydrogenation is one of the most important industrial operations, and reduced metals (mostly noble metals and a few inexpensive metals) generally serve as the catalyst to activate molecular H2. Herein we report oxygen-deficient tungsten oxide, such as WO2.72, is a versatile and efficient catalyst for the hydrogenation of linear olefins, cyclic olefins, and aryl nitro groups, with obvious advantages compared with non-noble metal nickel catalyst from the aspect of activity and selectivity. Density functional theory calculations prove the oxygen-deficient surface activates H2 very easily in both kinetics and thermodynamics. Testing on several oxygen-deficient tungsten oxides shows a linear dependence between the hydrogenation activity and oxygen vacancy concentration. Tungsten is earth-abundant, and WO2.72 can be synthesized in large scale using a low-cost procedure, which provides an ideal catalyst for industrial application. Because oxygen vacancy is a common characteristic of many metal oxides, the findings in this work may be extended to other metal oxides and thus provide the possibility for exploring a new type of hydrogenation catalyst.
- Song, Jiajia,Huang, Zhen-Feng,Pan, Lun,Zou, Ji-Jun,Zhang, Xiangwen,Wang, Li
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p. 6594 - 6599
(2015/11/18)
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- Method for Producing Adamantane
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A method for producing adamantane includes the steps of preparing a catalytic composition including an acidic ionic liquid and a co-catalyst and subjecting a tetrahydrodicyclopentadiene-containing component to isomerization in the presence of the catalytic composition to form adamantane. The acidic ionic liquid includes aluminum chloride and a quaternary onium compound selected from the group consisting of a quaternary ammonium halide, a quaternary phosphonium halide, and a combination thereof. The co-catalyst is an oxygen-containing reagent.
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Paragraph 0041
(2015/12/23)
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- The cyclic olefin-based polymer, selective hydrogenation method and manufacturing method thereof
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A cycloolefin-based copolymer and a hydrogenation process are disclosed, wherein the cycloolefin-based copolymer is prepared by using: a monomer which can be easily and economically obtained by hydrogenating dicyclopentadiene that occupies much of C5 fractions from naphtha cracking; or a monomer which can be obtained by chemically bonding three molecules of cyclopentadiene via Diels-Alder reactions and then hydrogenating the cyclopentadiene. The copolymer can be used in various fields as an amorphous transparent resin.
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Paragraph 0138
(2016/12/22)
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- Catalyst-free hydrogenation of alkenes and alkynes with hydrazine in the presence of oxygen
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A series of alkenes and alkynes was subjected to reduction with hydrazine hydrate in ethanol in the presence of oxygen. An efficient method was developed for the reduction of C-C double bonds and C-C triple bonds with diimide, generated in situ from hydrazine hydrate by oxidation with oxygen. The reduction process proceeded for 24-48? hours with high chemoselectivity and excellent yields. This reduction procedure offers synthetic advantages over metal-catalyzed hydrogenation as well as other systems. Georg Thieme Verlag Stuttgart New York.
- Menges, Nurettin,Balci, Metin
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p. 671 - 676
(2014/04/03)
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- Colloid and nanodimensional catalysts in organic synthesis: I. Investigation of hydrogenation selectivity of unsaturated compounds with hydrazine hydrate and aluminum hydride
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Results of investigation of selective hydrogenation of unsaturated carbon-carbon bonds with hydrazine hydrate or complex metal hydrides in the presence of metal nanoparticles are reported. Conditions of exhaustive and partial hydrogenation of some derivatives of norbornene, styrene, and unsaturated carboxylic acids are developed.
- Popov,Mokhov,Nebykov
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p. 444 - 448
(2014/05/20)
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- Highly selective mono-hydrogenation of dicyclopentadiene with Pd-nanoparticles
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In this paper, we present a new protocol to synthesize dihydrodicyclopentadienes (DHDCP), via mono hydrogenation of dicyclopentadiene. With the use of Pd-nanoparticles as catalysts the products are formed highly selective under mild conditions. The ratio between the DHDCP and the tetrahydrodicyclopentadiene (THDCP) can be shifted by variation of the hydrogen pressure from 7:1 to 1:8, with high conversions of over 85 %. The product DHDCP is an essential building block in co-polymerizations. Also we show an easy recycling concept for the nanocatalyst by phase separation. With simple filtration the solid products DHDCP and THDCP can be isolated and the liquid catalyst phase can directly be reused. Over all recycling runs a steady high conversion of about 75 % was observed.
- Behr, Arno,Manz, Vanessa,Lux, Adrian,Ernst, Andrea
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p. 241 - 245
(2013/07/27)
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- High temperature bromination Part XXIII: Bromination of octahydro-1H-indene and octahydro-1H-4,7-methanoindene
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Thermal and photobromination of octahydro-1H-indene and octahydro-1H-4,7-methanoindene were investigated. Three isomeric tetrabromides (1,3,4,7-tetrabromo-2,3,4,5,6,7-hexahydro-1H-indene) were formed along with a smaller amount of tribromoindane and a pentabromide by thermal bromination of octahydro-1H-indene. The thermodynamically most stable isomers were formed. Morover, thermal and photochemical bromination of octahydro-1H-4,7-methanoindene furnished bromides resulting regiospecifically from the allylic bromination of the five-membered ring. Furthermore, the double bond formed as the intermediate functional group was also brominated due to its pyramidalization. The mechanism proposed for the formation of product distribution was discussed. ARKAT-USA, Inc.
- Ozer, Melek Sermin,Kilbas, Benan,Balci, Metin
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p. 388 - 404
(2014/01/23)
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- Selective hydrogenation of alkenes under ultramild conditions
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SiliaCat Pd0 solid catalyst heterogeneously mediates at room temperature the selective hydrogenation of a wide variety of alkenes under hydrogen balloon conditions using a modest 0.1 mol % catalyst amount. The catalyst is recyclable with negligible leaching of valued palladium, providing the chemical industry with a suitable replacement for less selective metal-based catalysts.
- Pandarus, Valerica,Gingras, Genevieve,Beland, Francois,Ciriminna, Rosaria,Pagliaro, Mario
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experimental part
p. 1230 - 1234
(2012/07/28)
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- PROCESS FOR PRODUCING ADAMANTANE
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A method for producing adamantane by performing an isomerization reaction in two stages using endo-tetrahydrodicyclopentadiene and/or exo-tetrahydrodicyclopentadiene as a starting material, wherein in a first-stage isomerization reaction from endo-tetrahydrodicyclopentadiene (tricyclo[5.2.1.02,6]decane) to exo-tetrahydrodicyclaopentadiene (tricyclo[5.2.1.02,6]decane), an HF catalyst alone or two catalysts of an HF catalyst and a BF3 catalyst are used in the absence of a solvent; and in a second-stage isomerization reaction from exo-tetrahydrodicyclopentadiene (tricyclo[5.2.1.02,6]decane) to adamantane (tricyclo[3.3.1.13,7]decane), an HF catalyst and a BF3 catalyst are used in the absence of a solvent.
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Page/Page column 3; 6
(2011/02/19)
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- Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system
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The catalytic system Ni(COD)2/BF3·OEt2 has been studied in conversions of 1,5-cyclooctadiene under argon and ethylene atmosphere. It has been demonstrated that the catalytic system formed under argon exhibits a high effectiveness in cycloisomerization of 1,5-COD surpassing in this characteristic all known nickel complex catalysts (selectivity to bicyclo-[3.3.0]-octene-2 is up to 99.5% at 100% conversion). In the case of ethylene atmosphere the system produces mainly dimers (yield of cyclodimers above 70%). It has been shown that the catalytic system Ni(COD)2/BF3·OEt2 has the feature of "a living catalyst" consisting in resuming the initial activity with a new portion of 1,5-COD added when the monomer was fully exhausted. The main and side products of the 1,5-COD conversion have been identified with GC-MS and preparative liquid chromatography combined with NMR and IR spectroscopy. Based on EPR and IR spectroscopic data a mechanism for the catalytic performance of the Ni(COD)2/BF3·OEt2 system in argon or ethylene atmospheres is suggested. It has been shown that Ni(0) is oxidized by the Lewis acid to Ni(I) which is stabilized by substrate molecules in a mononuclear form without involvement of conventional organoelement entities. Three sorts of paramagnetic nickel species have been found: ionic complexes containing π-coordinated COD ligands; ionic complexes σ-bonded to COD; complexes as intimate pairs with BF4- counter ions. A mechanism for the catalytic conversion of 1,5-cyclooctadiene is proposed.
- Saraev,Kraikivskii,Matveev,Bocharova,Petrovskii,Zelinskii,Vilms,Klein, Hans-Friedrich
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scheme or table
p. 231 - 238
(2010/05/12)
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- PROCESS FOR ISOMERIZATION OF TETRAHYDRODICYCLOPENTADIENE USING SUPPORTED ACIDIC IONIC LIQUID AS A CATALYST
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A process for isomerization of tetrahydrodicyclopentadiene using a supported acidic ionic liquid as catalyst is provided. In the presence of the supported acidic ionic liquid, endo-tetrahydrodicyclopentadiene is isomerized to exo-tetrahydrodicyclo-pentadiene, wherein the supported acidic ionic liquid includes a porous support and an acidic ionic liquid, and the acidic ionic liquid includes an aluminum halide, and a quaternary ammonium halide or a quaternary phosphonium halide. The porous support is impregnated with the acidic ionic liquid. Furthermore, under different reaction conditions, the exo-tetrahydrodicyclopentadiene product can be isomerized to adamantane in the presence of such a supported acidic ionic liquid.
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Page/Page column 6
(2010/10/19)
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- Stereoselectivity in the rhodium-catalysed reductions of nonconjugated dienes
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The stereochemical course of rhodium-catalysed addition of hydrogen and catecholborane to bicyclo[2.2.1]heptadiene, and of hydrogen to a range of cyclic dienes has been analysed. For hydroboration, the overall catalytic reaction possesses exo-selectivity, but the initial step is endo-selective. For hydrogenation (deuteration), the first step may occur with either exo- or endo- selectivity, depending on the structure of the diene. This enables a distinction to be made between pathways involving prior dissociation of the diene, and direct addition to the complexed diene without full dissociation. The relative ease of hydrogenation of the first and second doublebonds varies markedly with reactant structure, and also depends on the choice of catalyst ligands. For dicyclopentadiene, hydrogenation of the cyclopentene double bond is accompanied by rapid alkene isomerisation, as revealed by deuterium addition. The asymmetric hydrogenation of acyclic skipped mesodienes is reported, demonstrating control of relative rates of the two sequential steps, with ees of up to 53% after the first reduction.
- Nguyen, Bao,Brown, John M.
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body text
p. 1333 - 1343
(2009/12/27)
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- Methods for purifying alkane liquids
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Methods for purifying liquid alkanes are provided. The methods produce alkanes having low absorbance, particularly at 193 nm. The alkane liquids are useful as immersion liquids in photomicrolithography employed for production of electronic circuits.
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Page/Page column 4
(2008/06/13)
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- Method for producing exo-tetrahydrodicyclopentadiene using ionic liquid catalyst
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An exo-tetrahydrodicyclopentadiene is produced from endo-tetrahydrodicyclopentadiene through isomerization reaction. An acidic ionic liquid is used in the isomerization. The isomerization of endo-tetrahydrodicyclopentadiene gives a reaction conversion and a selectivity both higher than 99%. Besides, the ionic liquid used is environmental-friendly and recyclable.
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Page/Page column 1-2
(2008/06/13)
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- METHOD FOR PREPARING HIGH ENERGY FUELS
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A method for preparing the low carbon number petrochemical products along with the high energy fuels from pyrolysis gasoline is provided. In this method, the pyrolysis gasoline is used as feedstock, and the reactive non-aromatic, unsaturated moieties, and the sulfur impurity contained in the pyrolysis gasoline are removed. Then the stabilized feedstock is used to produce C5 olefins, C6-C9 aromatic hydrocarbons as petrochemical products, and C10+ hydrocarbons as precursors of high energy fuels. Upon acid catalytic isomerization, or upon crystallization followed by acid catalytic isomerization, the C10+ hydrocarbons as precursors of high energy fuels are converted to exo-isomers as high energy fuels.
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Page/Page column 8
(2008/12/04)
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- METHOD FOR PRODUCING ADAMANTANE
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A method for producing adamantane includes isomerizing exo-tetrahydrodicyclopentadiene into adamantane in an acidic chloroaluminate ionic liquid composed of aluminum(III) trichloride and a quaternary ammonium halide having a quaternary ammonium cation selected from a group consisting of tetraalkylammonium, dialkylpyridinium, and trialkylimidazolium.
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Page/Page column 2
(2009/01/24)
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- PROCESS FOR PRODUCING ADAMANTANE
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The present invention provides a process of an industrially advantageous production of high-purity adamantane at a low cost and with a high efficiency by isomerizing trimethylenenorbornane contained in a raffinate obtained from a platfinate.
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Page/Page column 7
(2008/06/13)
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- The NiCl2-Li-Arene (cat.) Combination as Reducing System, Part 9: Catalytic Hydrogenation of Organic Compounds using the NiCl 2-Li-(Naphthalene or Polymer-Supported Naphthalene) (cat.) Combination
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The reaction of lithium powder, a catalytic amount of naphthalene or polymer-supported naphthalene, and anhydrous nickel(II) chloride, in THF at room temperature, generates a finely divided and very reactive nickel(0) which has been efficiently applied to the catalytic hydrogenation of different organic compounds such as alkenes, alkynes, carbonyl compounds, imines, organic halides, aromatic compounds, hydrazines, azoxy compounds, and N-oxides.
- Alonso, Francisco,Candela, Pablo,Gómez, Cecilia,Yus, Miguel
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p. 275 - 279
(2007/10/03)
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- Cobalt Nanoparticles on Charcoal: A Versatile Catalyst in the Pauson-Khand Reaction, Hydrogenation, and the Reductive Pauson-Khand Reaction
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(Matrix Presented) Dispersions of nanometer-sized cobalt particles with very high stability were prepared in charcoal and analyzed by electron microscopy and X-ray analysis. The resulting cobalt nanoparticles on charcoal (CNC) were successfully used as a catalyst for the carbonylative cycloaddition of alkyne, alkene, and carbon monoxide (Pauson-Khand reaction), hydrogenation, and the reductive Pauson-Khand reaction.
- Son, Seung Uk,Park, Kang Hyun,Chung, Young Keun
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p. 3983 - 3986
(2007/10/03)
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- Transformations of cycloalkanes under the action of organoaluminum compounds and transition metal complexes in the presence of polychloromethanes
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A catalytic system comprising an organoaluminum compound, polychloromethane, and a transition metal complex transforms cyclohexane into dimethyldecalins, cyclooctane into dimethyl-and ethylcyclohexanes, and endo-tricyclo[5.2.1.02.6]decane into its exo-isomer under mild conditions.
- Sadykov,Samokhina,Dzhemilev
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p. 1326 - 1329
(2007/10/03)
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- Hydrogenation of olefins with hydrated nickel chloride, lithium and a catalytic amount of naphthalene
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The reaction of different olefins or dienes with a mixture of nickel (II) chloride dihydrate, an excess of lithium powder and a catalytic amount of naphthalane (17 mol%) in THF at room temperature, leads to the formation of the corresponding alkanes. The incorporation of deuterium oxide to the nickel salt complex yields deuterated hydrocarbons. Finally, in the case of dienes as starting materials the method can serve for mono or dihydrogenation depending on the amount of nickel salt used.
- Alonso, Francisco,Yus, Miguel
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p. 6925 - 6928
(2007/10/03)
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- Kinetic isotope effect in the hydrogenation of tricyclo-(5,2,1,02.6)-deca-3,8-diene on platinum metals
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The hydrogenation of dicyclopentadiene 21.6)-deca-3,8-diene> by protium and deuterium on Pt, Pd, Ir, Rh, and Ru blacks in hexane at atmospheric or higher hydrogen pressures has been studied at 298-423 K.The kinetic isotope effect has been shown to vary from 1.33 to 2.50 according to the nature of the metal.The main product of complete hydrogenation is endo-tetrahydrodicyclopentadiene 2.6)-decane>: its yield under comparable conditions is higher in a deuterium atomosphere than in the presence of protium.
- Ualikhanova, A.,Temirbulatova, A. E.,Dembitskii, A. A.,Mailyubaev, B. T.,Korolev, A. V.
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p. 240 - 242
(2007/10/02)
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- The Adamantane Rearrangement of syn- and anti-Tricyclo2,5>decane. Part II. Rearrangements Initiated by Regioselective Formation of Carbocations at C(3) and C(9)
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The endo- and exo-alcohols 5-12 of syn- (1) and anti-tricyclo2,5>decane (2) were treated with BF3/Et3SiH (ionic hydrogenation) in order to study the behaviour of the corresponding regioselectively generated carbocations at C(3) (a (syn), b (anti) and C(9) (c (syn), d (anti)).The anti-hydrocarbon 2 is practically the sole product obtained starting with the four 3-alcohols (via a -> b from 5 and 6 (syn) and via b from 9 and 10 (anti)).The four 9-alcohols in each case yield a mixture of 2-endo,3-endo- (3) and 2-exo,3-exo-trimethylene-8,9,10-trinorbornane (4) (via c -> e from 7 and 8 (syn) and via d -> f from 11 and 12 (anti)), but no hydrocarbon 2, i.e. none of the 1,3-H shifts c -> a and d -> b is involved.
- Brossi, Marco,Ganter, Camille
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p. 848 - 858
(2007/10/02)
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- THE PHOTOCHEMICAL NUCLEOPHILE-OLEFIN COMBINATION, AROMATIC SUBSTITUTION REACTION (PART 2): METHANOL-CYCLIC OLEFINS, 1,4-DICYANOBENZENE
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Direct irradiation of acetonitrile-methanol (3:1) solutions of 1,4-dicyanobenzene and the cyclic olefins, cyclohexene, 1-methylcyclohexene, norbornene, and 2-methylnorbornene, leads to formation of regio- and stereoisomers of the 1:1:1 (alcohol : olefin : aromatic) adducts.This reaction can be photosensitized by electron transfer; addition of electron donors, biphenyl or phenanthrene, to the irradiation mixture generally increases the efficiency and yield of adduct formation.The efficiency of the reaction and the ratio of isomeric adducts are also affected by the addition of salts, particularly magnesium perchlorate.All of the possible regio- and stereoisomers from cyclohexene and 1-methylcyclohexene have been identified, two from cyclohexene and four from 1-methylcyclohexene.Three of the four possible isomers from norbornene were characterized; the endo, endo isomer was not detected.There are eight possible isomers from 2-methylnorbornene; six were detected and five have been isolated and identified.The two sterically hindered isomers, those having both the 4-cyanophenyl and the methoxy groups in the endo position, and exo-3-(4-cyanophenyl)-endo-2-methoxy-exo-2-methylnorbornane, were not characterized.The structures of the products were established largely on the basis of the 1H and 13C nuclear magnetic resonance spectra.The mechanism of the reaction is discussed, with emphasis on those factors that may affect the product ratio.The most striking observation is that the reaction is regioselective when magnesium perchlorate is added to the irradiation mixture.
- Arnold, Donald R.,Snow, Miles S.
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p. 3012 - 3026
(2007/10/02)
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