F+:Highly flammable;
109-67-1Relevant articles and documents
Photooxidation of n-heptanal in air: Norrish type I and II processes and quantum yield total pressure dependency
Tadic, Jovan M.,Juranic, Ivan O.,Moortgat, Geert K.
, p. 135 - 140 (2002)
Dilute mixtures of n-heptanal in synthetic air (up to 100 ppm) were photolyzed with fluorescent UV lamps (275-380 nm) at 298 K. The main photooxidation products, identified and quantitatively analyzed by FTIR spectroscopy, were pent-1-ene, CO, vinyl alcoh
Synthesis and catalytic investigation of organophilic Pd/graphite oxide nanocomposites
Mastalir,Szabó,Király,Dékány
, p. 104 - 107 (2012)
Low-loaded, organophilic Pd/graphite oxide (Pd/GO) nanocomposites were synthesized from different Pd complex precursors by applying graphite oxide as a host material and tetradecyltrimethylammonium bromide (C14TAB) as a stabilizer. Structural investigation of the Pd/GO samples was performed by ICP-AES, XRD, N2 sorption and TEM measurements. It was found that monodispersed Pd nanoparticles were formed, ranging in size between 1 and 6 nm, both on the external surface and in the interlamellar space of GO. The samples proved to be highly active and selective catalysts for liquid-phase alkyne hydrogenations. The variation in the catalytic performances was attributed to the difference in the amount of interlamellar Pd particles, which participated in the reactions as active sites.
A Mechanistic Study of the Rhodium-Catalyzed Cyclization of 4-Hexenals. Reactions of Deuterio-4-hexenals
Campbell, Richard E.,Lochow, Charles F.,Vora, Krishnakant P.,Miller, Roy G.
, p. 5824 - 5830 (1980)
In independent experiments, four carbons in the 4-pentenal skeleton have been labeled with deuterium or methyl and the fate of each label has been determined as the pentenal was transformed into a cyclopentanone derivative by RhCl(PPh3)3 (1) at 24-26 deg C.The catalyst converted 4-hexenal to 2-methylcyclopentanone (2) in CHCl3 and C6H6.Approximately equivalent amounts of hydrocarbon decarbonylation products and RhCl(CO)(PPh3)2 were also formed. 3-Methyl-4-pentenal was isomerized to 3-methylcyclopentanone by 1. 4-Hexenal possessing deuterium at C-2 was isomerized to 2 which contained deuterium at C-5. trans-4-Hexenal-1-d was cyclized to 2-3-d and 2-2-d in 9:1 ratio when the reaction was carried to a low conversion.The deuterium in the 2-3-d product was found to be cis to the C-2 CH3 group. cis-4-Hexenal-1-d was isomerized by 1 to afford 2-3-d possessing deuterium trans to the C-2 CH3 group.NMR analyses of these products were assisted by the synthesis and characterization of 2-cis-2,3-d2 by treatment of 2-methylcyclopent-2-en-1-one with D2 and 1.The 2-cis-2,3-d2 could be converted to a 1:1 mixture of 2-3-d diastereomers on treatment with HCl in MeOH/H2O.The result demonstrated that the cyclization of 4-hexenal-1-d occurred by a syn addition of the C-D bond to the olefinic bond to generate 2-3-d.The presence of C2H4 in reactin mixtures of 1 and 4-hexenal-1-d resulted in the formation of substantial 2-d0 and C2H3D.The deuterium locations in the 1-pentene, 2-pentene, and ethylcyclopropane decarbonylation products derived from reaction of 4-hexenal-1-d with 1 were determined.The results were interpreted in terms of a hydroacylation mechanism involving an acylrhodium(III) hydride complex and organometallic intermediates derived therefrom.The hydroacylation and decarbonylation products appear to be generated via common intermediates.
Faujasite silicalites for oxidative dehydrogenation of n-octane: Influence of alkali metals, gallium, and boron on catalyst activity
Ndlela, Siyabonga S.,Friedrich, Holger B.,Cele, Mduduzi N.
, (2021)
The sol-gel method was used to synthesize faujasite type silicalites bearing gallium and boron in the framework. Barium and sodium were used as charge balancing cations since isomorphic substitution of Si4+ by Ga3+ or B3+ results in a negative excess charge of the framework. The successful synthesis of this type of silicalites (GaBaY-S, BBaY-S, GaBBaY-S(IE), GaNaY-S) was confirmed using powder-XRD. SEM analysis showed that the morphology of the catalysts with respect to particle size depended on the framework metals and the charge balancing cation used. Framework Ga containing catalysts showed smaller particle size compared to B containing catalysts. Sodium also yielded a smaller particle-sized catalyst compared to barium. The catalysts were tested in the continuous flow oxidative dehydrogenation (ODH) of n-octane, and the catalytic results showed dependence on the active metal reducibility and acid-base character of the catalysts. At iso-conversion of 8 ± 1 %, the least acidic BBaY-S gave the highest selectivity to octenes (40 %) and the lowest selectivity to COx (28 %), and the most acidic GaNaY-S showed the opposite results with octenes at 17 % and COx at 56 %. The catalysts (BaBY-S and GaBBaY-S(IE) with least total acidity had the greatest quantity of strong acid sites which were attributed to Lewis acid sites, confirmed by the pyridine IR analysis. The GaNaY-S, with the highest total acidity, had the least strong acid sites.
Photolysis of heptanal
Paulson, Suzanne E.,Liu, De-Ling,Orzechowska, Grazyna E.,Campos, Luis M.,Houk
, p. 6403 - 6408 (2006)
Photolysis of heptanal is investigated from an experimental and theoretical point of view. Photoexcited heptanal is believed to undergo rapid intersystem crossing to the triplet manifold and from there undergoes internal H-abstraction to form biradical intermediates. The favored γ-H abstraction pathway can cyclize or cleave to 1-pentene and hydroxyethene, which tautomerizes to acetaldehyde. Yields of 1-pentene and acetaldehyde were measured at 62 ± 7% and 63 ± 7%, respectively, relative to photolyzed heptanal. Additionally, small quantities of hexanal and hexanol were observed. On the basis of combined experimental and theoretical evidence, the remaining heptanal photolysis proceeds to form an estimated 10% HCO + hexyl radical and 30% cyclic alcohols, particularly 2-propyl cyclobutanol and 2-ethyl cyclopentanol.
The Selective Conversion of n-Pentane into Pent-1-ene via Trihydro(trans-penta-1,3-diene)bis(triarylphosphine)rhenium
Baudry, Denise,Ephritikhine, Michael,Felkin, Hugh,Zakrzewski, Janusz
, p. 1235 - 1236 (1982)
Treatment of n-pentane with heptahydridobis(triarylphosphine)rhenium and 3,3-dimethylbutene gives trihydrido(trans-penta-1,3-diene)bis(triarylphosphine)rhenium; trimethyl phosphite converts this, with high selectivity, into pent-1-ene.
Photolysis and Radiolysis of Cyclopentane in the Liquid Phase
Ausloos, P.,Lias, S. G.,Rebbert, R. E.
, p. 2322 - 2328 (1981)
The liquid-phase photolysis of cyclopentane has been investigated at energies below (7.6, 8.4 eV) and above (10.0, 11.6 eV) the ionization threshold (8.7 eV).The molecules excited by photon absorption and by charge recombination undergo four major dissoci
On the Mechanism of Oligomerization of Propylene by (C5Me5)2MCl2/Methylalumoxane Catalysts (M=Zr, Hf)
Mise, Takaya,Kageyama, Akiko,Miya, Shinya,Yamazaki, Hiroshi
, p. 1525 - 1528 (1991)
In the oligomerization of propylene by (C5Me5)2MCl2 (M=Zr, Hf)/methylalumoxane, formation of abnormal oligomers such as 1-pentene(C5), 2,4-dimethyl-1-pentene(C7), 4-methyl-1-heptene(C8), and 2,4,6-trimethyl-1-heptene(C10) besides normal oligomers such as 4-methyl-1-pentene(C6) and 4,6-dimethyl-1-heptene(C9) is indicative of the mixing of unusual β-CH3 and usual β-H transfer terminations from each growing carbon chain which was initiated by insertion of propylene into either M-H or M-Me bond.
Pt/[Fe]ZSM-5 modified by Na and Cs cations: An active and selective catalyst for dehydrogenation of n-alkanes to n-alkenes
Li, Xuebing,Iglesia, Enrique
, p. 594 - 596 (2008)
Pt clusters within [Fe]ZSM-5 channels provide active and stable sites for the selective catalytic dehydrogenation of n-alkanes to n-alkenes. Cs and Na cations titrate acid sites and inhibit skeletal isomerization and cracking side reactions. The Royal Soc
Homogeneous catalytic transfer dehydrogenation of alkanes with a group 10 metal center
Khaskin, Eugene,Lew, Daniel L.,Pal, Shrinwantu,Vedernikov, Andrei N.
, p. 6270 - 6272 (2009)
Unambiguous catalytic homogeneous alkane transfer dehydrogenation was observed with a group 10 metal complex catalyst, LPtII(cyclo-C 6H10)H, supported by a lipophilic dimethyl-di(4-tert- butyl-2-pyridyl)borate anionic ligand and tert-butylethene as the sacrificial hydrogen acceptor.
Catalytic dehydroisomerization of n-alkanes to isoalkenes
Li, Xuebing,Iglesia, Enrique
, p. 134 - 137 (2008)
An equilibrated mixture of pentene isomers was produced by dehydroisomerization of n-pentane on catalysts consisting of Pt clusters within [Fe]ZSM-5 channels. These catalysts showed high isomerization rates, excellent stability even without added H2
REACTIONS OF ORGANOMAGNESIUM COMPOUNDS WITH ALLYL SULFONES, CATALYZED BY TRANSITION METAL SALTS
Ibragimov, A. G.,Minsker, D. L.,Saraev, R. A.,Dzhemilev, U. M.
, p. 2104 - 2107 (1983)
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Dehydrobromination of Secondary and Tertiary Alkyl and Cycloalkyl Bromides with 1,8-Diazabicycloundec-7-ene. Synthetic Applications
Wolkoff, Peder
, p. 1944 - 1948 (1982)
The alkene proportions from the dehydrohalogenation of eight secondary and six tertiary aliphatic bromides, four 1-bromo-1-alkylcycloalkanes, three dibromobutanes, and 2-hexyl chloride and iodide with the hindered amidine 1,8-diazabicycloundec-7-ene (DBU) have been determined.For secondary bromides, the ratios of the more substituted alkene (Saytzeff product) to less substituted alkene (Hofmann product) are on the order of 9:1; for tertiary bromides, the corresponding ratios are 2-3:1 for aliphatic systems and >6:1 for cycloalkyl systems.The presence of a tertiary or benzylic β-H favors the Saytzeff product.Chain branching or elongation of the tertiary aliphatic bromides has only a small effect upon the regioselectivity.Activation of the β-H with a bromine atom considerably reduces the regioselectivity.For 2-halohexanes, the proportion of Saytzeff product increases in the order chloride bromide iodide, while the trans/cis ratio increases in the same order from 4.9 to 9.Reduced regio- and stereoselectivities were observed when 2-hexyl p-toluenesulfonate was treated with DBU.The thermolysis of the same compound gave a mixture of 1-, 2-, and 3-hexene
HYDROGENATION OF CONJUGATED DOUBLE BONDS OF trans-1,3-PENTADIENE CATALYZED BY Rh2Cl2(CO)4 IN SOLUTION AND ANCHORED TO γ-Al2O3
Lausarot, P. Michelin,Vaglio, G. A.,Valle, M.
, p. 111 - 119 (1981)
Hydrogenation under mild conditions (1 atm H2 and 60-80 deg C) of trans-1,3-pentadiene catalysed by Rh2Cl2(CO)4 in toluene solution and by Rh2Cl2(CO)4 anchored on γ-Al2O3 has been investigated.Both the homogeneous and the heterogenised catalysts display a good specificity towards hydrogenation of the external double bond of the conjugated diene system.A slow inactivation of the supported catalyst occurs during the hydrogenation, but it cannot be attributed to reaction of the catalyst with the substrate since it occurs also when Rh2Cl2(CO)4 is heated at 70 deg C under 1 atm H2.Partial substitution of CO ligands of Rh2Cl2(CO)4 by triphenylphosphine leads to a reduction of the activity of the homogeneous catalyst but does not alter its specificity.Triphenylphosphine can either increase or decrease the activity of the heterogenised catalyst depending on whether its introduction into the system precedes or follows the anchorage of Rh2Cl2(CO)4 on Al2O3.
PENTENE FORMATION FROM PROPIONALDEHYDE ADSORBED ON Rh-Y ZEOLITE
Takahashi, Nobuo,Sato, Yoshio,Kobayashi, Masayoshi
, p. 1067 - 1068 (1984)
Pentene formation is observed during desorption of propionaldehyde from Rh-Y zeolite into a helium stream, while neither Na-Y zeolite nor H-Na-Y zeolite is effective for pentene formation.
RATIONAL TEST FOR POSSIBLE ZINCACYCLOBUTANE ION IN THE GUSTAVSON REACTION
Johnson, Thomas H.,Hefty, Elaine C.
, p. 23 - 33 (1981)
The possibility of obtaining a zincacyclobutane intermediate in the Gustavson reaction was hypothesized to explain the formation of olefins obtained in this reaction.A select group of substrates was investigated in which the formation of olefin products could be explained if one invoked the intermediacy of a zincacyclobutane, but would be difficult to explain in the absence of such an intermediate.A deuterium-labeled substrate was also investigated and the olefins obtained from its reaction with zinc were found to closely follow the deuterium-labeling pattern obtainedfrom the decomposition of the analogous deuterium-labeled platinacyclobutane.
SELECTIVE HYDROGENATION OF CARBON MONOXIDE ON SUPPORTED Rh CATALYSTS PREREDUCED IN SITU WITH H2O AND CO OR H2
Iwasawa, Yasuhiro,Hayasaka, Toshiaki,Ogasawara, Sadao
, p. 131 - 134 (1982)
Carbon monoxide was selectively converted to ethylene and propylene (>80percent of C1-C6 hydrocarbons produced) at 433-447 K over SiO2-supported Rh catalyst prereduced in situ with a CO-H2O mixture, while another Rh catalyst obtained by the pretreatment in situ with a H2-H2O mixture yielded ethanol and acetaldehyde at a higher selectivity by a factor of about 100 at 453 K than a usual Rh(0) catalyst reduced with H2 alone.
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Hill et al.
, (1955)
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Timofeewa,Schuikin
, p. 570;engl.Ausg.S.552 (1958)
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Skell,Maxwell
, p. 3963,3964 (1962)
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Tethering of a Phosphinidene Stabilised Cluster to Oxide Supports
Cook, Stephen L.,Evans, John
, p. 713 - 715 (1983)
The complex (μ-H)2Ru3(CO)93-PCH2CH2Si(OEt)3> (1a) has been supported on SiO2, Al2O3, TiO2, MgO, and ZnO; the phosphinidene ligand stabilises the cluster under catalytic conditions.
Selective aerobic oxidation in supercritical carbon dioxide catalyzed by the H5PV2Mo10O40 polyoxometalate
Maayan, Galia,Ganchegui, Benjamin,Leitner, Walter,Neumann, Ronny
, p. 2230 - 2232 (2006)
Selective aerobic oxidation of benzylic alcohols and of activated aromatic hydrocarbons occurs in supercritical CO2 as reaction medium using H5PV2Mo10O40 as a quasi-heterogeneous catalyst without further additives or co-solvents; efficient recycling is possible and no metal leaching is detectable in the product stream. The Royal Society of Chemistry 2006.
A Photochemical Source of Real Alkylcarbenes
Glick, HC,Likhotvorik, Igor R.,Jones, Maitland
, p. 5715 - 5718 (1995)
Treatment of 7,7-dibromodibenzobicycloheptane with di-tert-butylcuprate or dibutylcuprate, followed by quenching with water, led to exo- and endo-7-monoalkyldibenzobicycloheptanes.Photolysis through either quartz or Pyrex gave the products of intramolecular reactions of the corresponding alkylcarbenes.The temperature dependence of the products formed from tert-butylcarbene was verified, and butylcarbene was trapped intermolecularly. - Keywords: carbenes, retrocycloadditions, insertion reactions.
HYDROGENATION OF PIPERYLENE ON CATIONIC FORMS OF VARIOUS ZEOLITES
Kharlamov, V. V.,Kharatishvili, N. G.,Borisov, Yu. A.,Slyunyaev, P. I.,Minachev, Kh. M.
, p. 1044 - 1049 (1980)
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CATALYTIC HYDROCARBON DEHYDROGENATION
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Paragraph 0061; 0062; 0122; 0123, (2021/03/13)
A catalyst for dehydrogenation of hydrocarbons includes a support including zirconium oxide and Linde type L zeolite (L-zeolite). A concentration of the zirconium oxide in the catalyst is in a range of from 0.1 weight percent (wt. %) to 20 wt. %. The catalyst includes from 5 wt. % to 15 wt. % of an alkali metal or alkaline earth metal. The catalyst includes from 0.1 wt. % to 10 wt. % of tin. The catalyst includes from 0.1 wt. % to 8 wt. % of a platinum group metal. The alkali metal or alkaline earth metal, tin, and platinum group metal are disposed on the support.
Method for eliminating hydrogen chloride by catalytic cracking of chloralkane
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Paragraph 0142-0147, (2020/08/06)
The invention discloses a method for eliminating hydrogen chloride by catalytic cracking of chloralkane, comprising the following steps of: carrying out a cracking reaction on chloralkane under the action of a biomass-based nitrogen-doped carbon catalyst to eliminate hydrogen chloride so as to prepare corresponding olefin, wherein the biomass-based nitrogen-doped carbon catalyst is prepared by carbonizing biomass or a mixture of biomass and a nitrogen source at 400-1000 DEG C, and the biomass is selected from at least one of bamboo processing leftovers, wood processing leftovers, plant straws,plant leaves, cereals, beans, cereal processing leftovers, bean processing leftovers and livestock manure. The method disclosed by the invention has the advantages of simple preparation process, easily available raw materials, low cost, strong process controllability, easiness in large-scale production, high catalytic cracking conversion rate of the chloralkane, high product selectivity, low energy consumption and the like.
