108-10-1Relevant articles and documents
Palladium catalyzed mild reduction of α,β-unsaturated compounds by triethylsilane
Mirza-Aghayan, Maryam,Boukherroub, Rabah,Bolourtchian, Mohammad,Rahimifard, Mahshid
, p. 5113 - 5116 (2007)
The palladium(II) chloride/triethylsilane system has been successfully applied for the selective hydrogenation of the carbon-carbon double bond of α,β-unsaturated ketones to yield the corresponding saturated carbonyl compounds. The reaction takes place under mild conditions and affords high yields.
2-Phenylbenzothiazoline as a Reducing Agent in the Conjugate Reduction of α,β-Unsaturated Carbonyl Compounds
Chikashita, Hidenori,Miyazaki, Makoto,Itoh, Kazuyoshi
, p. 308 - 310 (1984)
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Selective deoximation using alumina supported potassium permanganate
Chrisman, William,Blankinship, Michael J,Taylor, Brady,Harris, Clifford E
, p. 4775 - 4777 (2001)
Ketoximes are converted to the parent ketones in good yields when treated with potassium permanganate supported on neutral alumina (ASPP). An optimized procedure has been developed, the simple work-up minimizes loss of product and oximes have been selectively oxidized in the presence of alkenes.
Alkoxy radical isomerization products from the gas-phase OH radical- initiated reactions of 2,4-dimethyl-2-pentanol and 3,5-dimethyl-3-hexanol
Atkinson,Aschmann
, p. 528 - 536 (1995)
The products of the gas-phase reactions of the OH radical with 2,4- dimethyl-2-pentanol and 3,5-dimethyl-3-hexanol in the presence of NO(x) have been determined at atmospheric pressure of air and 296 ± 2 K to assess the occurrence and importance of alkoxy radical isomerization. The products identified and quantified and their formation yields were as follows: from 2,4-dimethyl-2-pentanol: acetone, 0.92 ± 0.15; 2-methylpropanal, 0.209 ± 0.022; 4-methyl-2-2-pentanone, 0.046 ± 0.008; and 4-hydroxy-4-methyl-2- pentanone, 0.116 ± 0.018; from 3,5-dimethyl-3-hexanol: acetone, 0.120 ± 0.029; 2-butanone, 0.275 ± 0.021; 2-methylpropanal, 0.169 ± 0.016; 4- methyl-2-pentanone, 0.161 ± 0.012; and 4-hydroxy-4-methyl-2-pentanone, 0.250 ± 0.023. The observed formation of 4-hydroxy-4-methyl-2-pentanone provides conclusive evidence for the occurrence of isomerization of the alkoxy radicals (CH3)2C(OH)CH2C(O)(CH3)2 and CH3CH2C(CH3)(OH)CH2C(O)(CH3)2 via 1,5-H shifts. The reaction mechanisms are discussed, and isomerization rate constants for 1,5-H-atom abstraction from the -CH3 and -CH2- groups in the RCH2C(CH3)(OH)- CH2C(O)(CH3)2 alkoxy radicals (R = H and CH3) are derived.
Ethanolic or aqueous formic acid (1:1) - A new efficient reagent for the regeneration of ketones from phenylhydrazones
Chakrabarty, Manas,Khasnobis, Shampa
, p. 1361 - 1368 (1998)
50% Ethanolic or aqueous formic acid has been found to be extremely efficacious for the regeneration of aliphatic and aromatic ketones from phenylhydrazones.
Dehydration of 4-methylpentan-2-ol over lanthanum and cerium oxides
Auroux,Artizzu,Ferino,Monaci,Rombi,Solinas,Petrini
, p. 2619 - 2624 (1996)
Lanthanum and cerium oxides have been tested for the title reaction at 623 K and atmospheric pressure in a flow reactor. Lanthanum oxide (prepared from the corresponding nitrate) gives mainly 4-methylpent-1-ene (80% of the products). Similar results are observed with cerium oxide obtained from the corresponding hydroxide, whereas cerium oxide prepared from nitrate is less selective towards alk-1-enes. In addition to dehydration, dehydrogenation to 4-methylpentan-2-one is also observed to a limited extent for all the catalysts. Information on the acid-base properties of the samples was obtained by adsorption microcalorimetry of ammonia and carbon dioxide and correlated to reaction selectivities. Possible changes in the oxidation state of cerium ions due to the reaction atmosphere are considered. The present results are compared with former data for zirconia catalysts. Modification of cerium oxide via immersion in NaOH solution does not appear to be useful for improving alk-1-ene selectivity.
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De Puy
, p. 33,41 (1968)
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Baum,K.
, p. 7083 - 7089 (1968)
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Davis,Woodgate
, p. 65 (1966)
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Effect of metal modification of titania and hydrogen co-feeding on the reaction pathways and catalytic stability in the acetone aldol condensation
Quesada,Faba,Díaz, Eva,Ordó?ez, Salvador
, p. 133 - 144 (2019)
A stable performance of TiO2 catalysts for gas-phase acetone aldol condensation was observed when reduced metals were added (Pt or Ni, 1.5 wt%) and the reactions were conducted in presence of hydrogen. In both cases, the resulting metal-loaded catalysts are stable for 10 h, whereas continuous deactivation is observed for the parent TiO2 catalyst (573 K). Both the activation of the H2 molecule by metal nanoparticles and the change of the catalytic surface by metal insertion (in the case of Ni-loaded catalyst) enable suppressing oligomerization (by hindering enolates formation) and the strong adsorption of intermediates (by decreasing the concentration of high-strength acid-basic active sites), respectively. More interestingly, these metals allow to tune the selectivity of the reaction. Indeed, the Ni-loaded titania catalyst is highly selective for the synthesis of α,β-unsaturated ketones (selectivity to unsaturated C6 and C9 species >98%, at ~12% acetone conversion), whereas the Pt-loaded one is highly selective to the formation of saturated C6 and C9 ketones (MIBK and DIBK, with selectivities >95% at ~42% acetone conversion). The catalytic activity and stability of the two materials (Ni/TiO2 and Pt/TiO2) in both absence and presence of H2 are compared between them and with those of the parent TiO2. The results obtained by the reaction gas-phase analysis are supplemented through different solid characterization techniques (i.e., CO2-TPD and NH3-TPD, HRTEM, XPS, TPO, and DRIFTS).
Regiospecific solvent-free transfer hydrogenation of α,β-unsaturated carbonyl compounds catalyzed by a cationic ruthenium(II) compound
Naskar, Sipra,Bhattacharjee, Manish
, p. 465 - 467 (2007)
[(PPh3)2Ru(CH3CN)3Cl][BPh4] has been found to catalyze the selective reduction of double bonds in α,β-unsaturated ketones with high conversions when formic acid is the hydrogen donor.
CONVERSION OF ALKANES BY THE ACTION OF ACYL HALIDES AND AlBr3 UNDER MILD CONDITIONS
Akhrem, I. S.,Orlinkov, A. V.,Mysov, E. I.,Enaleeva, R. Ya.,Vol'pin, M. E.
, (1983)
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Intramolecular Activation of a N-Methyl C-H Bond by an Electron Rich Iridium Centre: a Novel Chemoselective Reduction Catalyst
Farnetti, Erica,Nardin, Giorgio,Graziani, Mauro
, p. 1264 - 1265 (1989)
The iridium complex > formed by intramolecular C-H oxidative addition, as shown by X-ray analysis, behaves as a chemoselective catalyst in hydrogen transfer reduction of α,β-unsaturated ketones to unsaturated alcohols.
The hydroxyl radical reaction rate constant and products of 3,5-dimethyl-1-hexyn-3-ol
Wells
, p. 534 - 544 (2004)
A bimolecular rate constant, κDHO, of (29 ± 9) × 10-12 cm3 molecule-1 s-1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,5-dimethyl-1-hexyn-3-ol (DHO, HC≡CC(OH)(CH3)CH2CH(CH3 2) at (297 ± 3) K and 1 atm total pressure. To more clearly define DHO's indoor environment degradation mechanism, the products of the DHO + OH reaction were also investigated. The positively identified DHO/OH reaction products were acetone ((CH3 2C=O), 3-butyne-2-one (3B2O, HC≡CC(=O)(CH3)), 2-methyl-propanal (2MP, H(O=)CCH(CH3)2), 4-methyl-2-pentanone (MIBK, CH3C(=O CH2 CH(CH3)2), ethanedial (GLY, HC(=O C(=O)H), 2-oxopropanal (MGLY, CH3C(=O)C(=O)H), and 2,3-butanedione (23BD, CH3C(=O)C(=O)CH3). The yields of 3B2O and MIBK from the DHO/OH reaction were (8.4 ± 0.3) and (26 ± 2)%, respectively. The use of derivatizing agents O-(2,3,4,5,6-pentalfluorobenzyl)hydroxylamine (PFBHA) and N,O-bis (trimethylsilyl)trifluoroacetamide (BSTFA) clearly indicated that several other reaction products were formed. The elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible DHO/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.
One-step synthesis of methyl isobutyl ketone from acetone and hydrogen over Cu-on-MgO catalysts
Chikan, Viktor,Molnar, Arpad,Balazsik, Katalin
, p. 134 - 143 (1999)
The one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen over Cu-on-MgO catalysts was studied at atmospheric pressure in a fixed bed continuous flow reactor. Catalysts with various copper loadings were prepared by impregnation and coprecipitation and characterized by BET and Cu(O) surface area measurements, XRD, SAXS, thermal analysis, and basicity measurements. A 3.46% Cu-on-MgO prepared by coprecipitation, calcined at 723 K for 4 h, and pretreated in hydrogen (673 K, 1 h) showed high and stable activity and selectivity in the production of MIBK. Under the best conditions (553 K reaction temperature, 15% molar excess of hydrogen to acetone, and 1920 ml h-1 gcat-1 space velocity) MIBK is formed in 45-48% yield (60-80% conversion and 60-75% selectivity) over a period of 24 h-on-stream. The results of deuterium labeling studies point to metallic sites catalyzing deuterium exchange and basic sites catalyzing dimerization of acetone, leading eventually to MIBK with high deuterium content. A comparison of deuterium contents of acetone, mesityl oxide (MO), and MIBK shows that the surface deuterium pool is highly diluted with hydrogen, formed during the exchange process. Deuterium incorporation during the saturation of the carbon-carbon double bond of MO to form MIBK, therefore, is less than expected. Formation of diisobutyl ketone with very low deuterium content is suggested to result from the involvement of strongly bound surface intermediates with long residence time not allowing exchange process.
1,3-Dichloro-5,5-dimethylhydantoin (DCDMH) as a new oxidizing agent for the facile and selective oxidation of oximes to their carbonyl compounds
Khazaei, Ardeshir,Manesh, Abbas Amini
, p. 1017 - 1020 (2005)
Oximes are converted to the parent carbonyl compounds in good yields when treated with 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) (1). An optimized procedure has been developed; the simple work-up minimizes loss of product and oximes have been selectively oxidized in the presence of alcohols and alkenes.
Copper(I)-catalysed Conjugate Reduction of α,β-Unsaturated Carbonyl Compounds by Lithium Aluminium Hydride
Tsuda, Tetsuo,Fujii, Tomoyuki,Kawasaki, Kaoru,Saegusa, Takeo
, p. 1013 - 1014 (1980)
CuI catalyses an efficient conjugate reduction of α,β-unsaturated carbonyl compounds by LiAlH4 in the presence of hexamethylphosphoric triamide at -78 degC.
Oxidative cleavage of oximes with silica-gel-supported chromic acid in nonaqueous media
Ali, Mohammed Hashmat,Greene, Stacie,Wiggin, Candace J.,Khan, Saira
, p. 1761 - 1767 (2006)
A simple procedure for a clean and high-yielding oxidative deoximation of benzaldoximes and ketoximes using a silica-gel-supported chromic acid reagent has been developed. This solid-supported reagent allows us to carry out this reaction in nonaqueous dichloromethane reaction media. Copyright Taylor & Francis Group, LLC.
Catalytic synthesis of cumene from benzene and acetone
Shutkina,Ponomareva,Ivanova
, p. 20 - 26 (2013)
The reaction of benzene hydroalkylation with acetone on bifunctional catalysts has been studied and the principal features of the process have been revealed, wherein the catalysts contain a copper oxide-copper chromite binary system as a hydrogenating component and BEA, MOR, FAU, or MFI zeolite as an alkylating component. It has been found that the use of the catalyst based on the mixed copper-chromium oxide and mordenite, running the process at 150 C and 3 MPa, and feedstock dilution with benzene (C6H6: C 3H6O = 9: 1) facilitate increasing of the yield of cumene as a main product.
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Rastetter,Frost
, p. 3353,3354,3355 (1979)
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Nickel catalyzed silane reductions of α, β - Unsaturated ketones and nitriles
Boudjouk, Philip,Choi, Seok-Bong,Hauck, Brian J.,Rajkumar, Amirthini B.
, p. 3951 - 3952 (1998)
Activated nickel, produced by the ultrasound-promoted reduction of nickel iodide with lithium, catalyzes the 1,4 addition of phenylsilane to α, β-unsaturated ketones and α, β-unsaturated nitriles to give, after hydrolysis, high yields of the products of 1, 2 hydrogenation.
Study on the selective hydrogenation of isophorone
Xu, Lei,Sun, Shaoyin,Zhang, Xing,Gao, Haofei,Wang, Wei
, p. 4465 - 4471 (2021)
3,3,5-Trimethylcyclohexanone (TMCH) is an important pharmaceutical intermediate and organic solvent, which has important industrial significance. The selective hydrogenation of isophorone was studied over noble metal (Pd/C, Pt/C, Ir/C, Ru/C, Pd/SiO2, Pt/SiO2, Ir/SiO2, Ru/SiO2), and non-noble metal (RANEY Ni, RANEY Co, RANEY Cu, RANEY Fe, Ni/SiO2, Co/SiO2, Cu/SiO2, Fe/SiO2) catalysts and using solvent-free and solvent based synthesis. The results show that the solvent has an important effect on the selectivity of TMCH. The selective hydrogenation of isophorone to TMCH can be influenced by the tetrahydrofuran solvent. The conversion of isophorone is 100%, and the yield of 3,3,5-trimethylcyclohexanone is 98.1% under RANEY Ni and THF. The method was applied to the selective hydrogenation of isopropylidene acetone, benzylidene acetone and 6-methyl-5-ene-2-heptanone. The structures of the hydrogenation product target (4-methylpentan-2-one, 4-benzylbutan-2-one and 6-methyl-heptane-2-one) were characterized using 1H-NMR and 13C-NMR. The yields of 4-methylpentan-2-one, 4-benzylbutan-2-one and 6-methyl-heptane-2-one were 97.2%, 98.5% and 98.2%, respectively. The production cost can be reduced by using RANEY metal instead of noble metal palladium. This method has good application prospects. This journal is
Hobbs,Houston
, p. 1254 (1954)
An exceptionally rapid and selective hydrogenation of 2-cyclohexen-1-one in supercritical carbon dioxide
Chatterjee, Maya,Yokoyama, Toshirou,Kawanami, Hajime,Sato, Masahiro,Suzuki, Toshishige
, p. 701 - 703 (2009)
Selective hydrogenation of 2-cyclohexen-1-one over Pt-MCM-41 proceeds at a very high rate and produces cyclohexanone with selectivity of 100% in a batch reactor; a marked increase in the reaction rate (TOF) from 2283 min-1 to 5051 min-1 is observed on increasing the pressure from 7 MPa to 14 MPa at 40°C. The Royal Society of Chemistry 2009.
Selective Catalytic Oxidation of Organic Compounds by Nitrogen Dioxide
Nyarady, Stefan A.,Sievers, Robert E.
, p. 3726 - 3727 (1985)
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PhIO-Mediated oxidative dethioacetalization/dethioketalization under water-free conditions
Du, Yunfei,Ouyang, Yaxin,Wang, Xi,Wang, Xiaofan,Yu, Zhenyang,Zhao, Bingyue,Zhao, Kang
, p. 48 - 65 (2021/06/16)
Treatment of thioacetals and thioketals with iodosobenzene in anhydrous DCM conveniently afforded the corresponding carbonyl compounds in high yields under water-free conditions. The mechanistic studies indicate that this dethioacetalization/dethioketalization process does not need water and the oxygen of the carbonyl products comes from the hypervalent iodine reagent.
Reduction of α,β-unsaturated carbonyl compounds and 1,3-diketones in aqueous media, using a raney ni-al alloy
Simion, Cristian,Mitoma, Yoshiharu,Katayama, Yumi,Simion, Alina Marieta
, p. 51 - 55 (2021/02/03)
The treatment of α,β-unsaturated carbonyl compounds and 1,3-diketones with Raney Ni-Al alloy in aqueous media yielded as major reaction products the corresponding saturated alcohols and/or the corresponding hydrocarbons, in a complete transformation of the starting material.