112-44-7Relevant articles and documents
One-pot conversion of primary alcohols to α-oxygenated alkanals with tempo in combination with molecular oxygen and ruthenium complex
Inokuchi, Tsutomu,Nakagawa, Keiichi,Torii, Sigeru
, p. 3223 - 3226 (1995)
Reaction of primary alcohols with an oxidizing system composed of 4-BzOTEMPO (2 equiv.), RuCl2(PPh3)3 as a catalyst, and molecular oxygen leads to concomitant oxidation and substitution, giving the corresponding α-oxygenated alkanals. Similar reaction of secondary alcohols terminates at the stage of oxidation of hydroxyl group, forming the ketones, selectively.
β-Cyclodextrins modified by alkyl and poly(ethylene oxide) chains: A novel class of mass transfer additives for aqueous organometallic catalysis
Badi, Nezha,Guégan, Philippe,Legrand, Fran?ois-Xavier,Leclercq, Lo?c,Tilloy, Sébastien,Monflier, Eric
, p. 8 - 14 (2010)
A novel class of β-cyclodextrins (β-CDs) bearing alkyl chains on the secondary face and poly(ethylene oxide) chains on the primary face was synthesized. Their interactions with two water-soluble derivatives of triphenylphosphane were investigated by 31P{1H} and 1H NMR. Their behaviour in rhodium-catalysed biphasic hydroformylation of 1-decene was evaluated and the best result was obtained with a β-CD bearing methyl groups on the secondary face and poly(ethylene oxide) chains on the primary face. This CD appeared to be more efficient than randomly methylated β-CD which is currently one of the best mass transfer additives for hydroformylation.
Polyether phosphite for hydroformylation of higher olefins in non-aqueous system and catalyst recovery
Liu, Xiaozhong,Li, Hongmei,Wang, Yanhua,Jin, Zilin
, p. 83 - 90 (2002)
A new rhodium catalyst recyling system for non-aqueous hydroformylation of 1-decene is described using a polyether phosphite, OPGPP with a polyether chain of over 19 ethylene glycol units. The corresponding rhodium complexes formed in situ are active for non-aqueous hydroformylation of 1-decene. The catalysts precipitated from the reaction mixture on cooling to room temperature or lower and were reused up to six times without obvious decrease in activity. P loss in the seventh reaction run was detected to be 0.92%. Complex OPGPP/Ru3(CO)3 formed in situ has also been proved to be a moderate catalyst for the non-aqueous hydroformylation of 1-decene. The catalysts retained considerable activity up to 87.1% after four successive reaction runs.
Continuous hydroformylation of 1-decene in an aqueous biphasic system enabled by methylated cyclodextrins
Dreimann, J. M.,Künnemann, K. U.,Lange, D.,Monflier, E.,Schurm, L.,Seidensticker, T.,Tilloy, S.,Vogt, D.
, p. 3809 - 3819 (2020)
For the first time, randomly methylated β-cyclodextrin was applied as the mass transfer agent in a continuous process. Considering the example of the Rh-catalyzed hydroformylation of 1-decene, process development was shown, where cyclodextrin was used together with a catalyst system that was continuously recovered and recycled using an aqueous biphasic system. In initial experiments, water-soluble and commercially available Rh/TPPTS and Rh/sulfoxantphos catalyst systems were scaled up from 50 ml into 1000 ml high-pressure autoclave systems to demonstrate their scalability. Both these systems were compared, and they afforded excellent chemoselectivity (>99percent) toward the desired linear aldehyde product. In particular, higher regioselectivity (up to 31) was achieved for the Rh/sulfoxantphos system. Investigations regarding the long-term stability of the mass transfer agent and both catalyst systems were carried out in a continuously operated miniplant process. It was shown that the process could be successfully operated under the steady state for over 200 h with chemoselectivity of >97percent toward the desired aldehyde product. Simultaneously, extremely low Rh leaching (total: 0.59percent) was observed over the entire period of 200 h.
TEMPO radical polymer grafted silicas as solid state catalysts for the oxidation of alcohols
Saito, Kei,Hirose, Koji,Okayasu, Teruyuki,Nishide, Hiroyuki,Hearn, Milton T. W.
, p. 9752 - 9756 (2013)
TEMPO polymer-grafted silicas were synthesized by "grafting from" and "grafting to" methods using RAFT polymerization, and their catalytic activities as a new class of solid state catalyst for oxidation reactions with alcohols demonstrated.
Rhodium-BiPhePhos catalyzed hydroformylation studied by operando FTIR spectroscopy: Catalyst activation and rate determining step
J?rke, Andreas,Seidel-Morgenstern, Andreas,Hamel, Christof
, p. 10 - 14 (2017)
The homogeneously rhodium catalyzed hydroformylation of 1-decene was studied using operando FTIR spectroscopy. The bulky chelating diphosphite ligand BiPhePhos was used for catalyst modification. Special emphasis was given to the transformation of the Rh-precursor Rh(acac)(CO)2 to the activated HRh(BiPhePhos)(CO)2 catalyst. Under hydroformylation conditions, this complex was found to be the most abundant catalyst species over a wide range of olefin conversion. Other inactive or non-selective rhodium species were not detectable. Analysis of the turnover frequency revealed a first order dependence of the hydroformylation rate with respect to the concentration of 1-decene. These findings indicate that the coordination of the olefin to the Rh-BiPhePhos catalyst is determining the hydroformylation rate of 1-decene.
Rhodium catalyzed hydroformylation of 1-decene in low melting mixtures based on various cyclodextrins and N,N′-dimethylurea
Ferreira, Michel,Jér?me, Fran?ois,Bricout, Hervé,Menuel, Stéphane,Landy, David,Fourmentin, Sophie,Tilloy, Sébastien,Monflier, Eric
, p. 62 - 65 (2015)
Different low melting mixtures (LMMs) based on N,N′-dimethylurea (DMU) and various cyclodextrin (CD) derivatives were synthetized. The melting point was weakly affected by the size and the chemical modification of CD. By contrast, the chemical modification of CD led to a decrease in viscosity of the LMMs. These mixtures were evaluated as solvent in rhodium-catalyzed hydroformylation reaction of 1-decene. The LMM based on DMU/RAME-β-CD (70/30) allowed reaching the highest catalytic activity (1980 h- 1). The influence of several factors was studied and it was established that the conversion increased with the 1-decene solubility and decreased with the LMM viscosity.
A New Oxidizing System for Aromatic Alcohols by the Combination of N-Oxoammonium Salt and Electrosynthesized Tetraalkylammonium Tribromide
Inokuchi, Tsutomu,Matsumoto, Sigeaki,Fukushima, Mitsuhiro,Torii, Sigeru
, p. 796 - 800 (1991)
A combination of 2,2,6,6-tetramethyl-1-piperidinyloxyl and tetraalkylammonium tribromides (R4NBr3), which are available from the corresponding tetraalkylammonium bromides via electrooxidation with potassium bromide, has proved to be useful for oxidations of primary and secondary alcohols to the corresponding aldehydes and ketones, respectively.The oxidation reaction proceeds smoothly even with a 0.5-1.0 molpercent of N-oxyl compounds and 1.5-2.0 equivalents of tetraalkylammonium tribromides in an aqueous-organic two-phase solution buffered at pH 8.0-8.6.This recyclable oxidant/co-oxidant combination system may involve the formation of N-oxoammonium salts, actual oxidizing agents of alcohols, by the action of hypobromite species generated from R4NBr3 in the binary solution.Utility of the method is highlighted by the selective oxidation of benzylic alcohols bearing electron-releasing groups on the aromatic nucleus to the corresponding aldehydes or ketones without any bromination and overoxidation.
Low melting mixtures based on β-cyclodextrin derivatives and N,N′-dimethylurea as solvents for sustainable catalytic processes
Jerome, Francois,Ferreira, Michel,Bricout, Herve,Menuel, Stephane,Monflier, Eric,Tilloy, Sebastien
, p. 3876 - 3880 (2014)
β-Cyclodextrin series and N,N′-dimethylurea formed low melting mixtures able to immobilize organometallic species based on sulfonated phosphanes. Hydroformylation and Tsuji-Trost reactions were efficiently performed in these new solvents which led to new recyclable catalytic systems. This journal is the Partner Organisations 2014.
Cetyltrimethylammonium bromochromate: A new and efficient oxidant for organic substrates
Ghammamy, Shahriar,Eimanieh, Hossein,Mohammady, Mohammad Kazem
, p. 601 - 607 (2007)
Cetyltrimethylammonium bromochromate is a versatile reagent for the effective and selective oxidation of organic substrates, particularly for alcohols, under mild conditions. Copyright Taylor & Francis Group, LLC.
