6140-65-4Relevant academic research and scientific papers
Synthesis of Adipic Aldehyde by n-Selective Hydroformylation of 4-Pentenal
Mormul, Jaroslaw,Mulzer, Michael,Rosendahl, Tobias,Rominger, Frank,Limbach, Michael,Hofmann, Peter
, p. 4102 - 4108 (2015/09/01)
Several phosphine and phosphite ligands were tested in the hydroformylation of 4-pentenal to adipic aldehyde, a versatile starting material for industrially very relevant compounds. By varying the ligand structure we were able to increase the selectivity toward adipic aldehyde to >95%. Additionally, two molecular structures of important catalytic intermediates [(bisphosphite)RhH(CO)2] and one structure of a previously unknown catalyst decomposition product were obtained. (Chemical Equation Presented).
Continuous-flow synthesis of adipic acid from cyclohexene using hydrogen peroxide in high-temperature explosive regimes
Damm, Markus,Gutmann, Bernhard,Kappe, C. Oliver
, p. 978 - 982 (2013/07/27)
Safe only in a microreactor! The synthesis of adipic acid from cyclohexene by tungstic acid-catalyzed oxidation using hydrogen peroxide following the classical Noyori protocol can be accomplished in good yields with residence times as short as 20 min at 140 °C using a safe and scalable microreactor environment. Under these intensified conditions the use of a phase-transfer catalyst is not required. Copyright
Oxidative cleavage of vic-diols to aldehydes with dioxygen catalyzed by Ru(PPh3)3Cl2 on active carbon
Takezawa, Eiichiro,Sakaguchi, Satoshi,Ishii, Yasutaka
, p. 713 - 715 (2008/02/11)
Formula presented A variety of vic-diols were first successfully cleaved to the corresponding aldehydes with dioxygen catalyzed by Ru(PPh3)3Cl2 on active carbon in fair to good yields. For example, treatment of 1,2-octandiol and 1,2-cyclooctanediol with dioxygen in the presence of Ru(PPh3)3Cl2/C in PhCF3 at 60°C for 15 h produced heptanal and 1,8-octanedial in 77% and 76% yields, respectively.
Two-phase Hydroformylation of Buta-1,3-diene and Hydrocarbon Mixtures Containing Buta-1,3-diene
Fell, Bernhard,Hermanns, Peter,Bahrmann, Helmut
, p. 459 - 467 (2007/10/03)
The two-phase hydroformylation of buta-1,3-diene with (HRh(CO)[P(m-C6H4SO3Na) 3]3) the Kuntz catalyst system with excess P(m-C6H4SO3Na)3) gives high yields of C5-monoaldehydes. Main product in this mixture is the reactive trans- and cis-pent-3-enal. In consecutive reactions the pent-3-enal is partially hydrogenated to n-pentanal, but also - favoured by the protolytic milieu of the two-phase reaction - aldol condensated to 2-propenylheptadienal. The hydrogenation product of the propenylheptadienal, 2-propylheptanol-1, is a good plasticizer alcohol with a wanted low vapour pressure. Especially promising is the two-phase hydroformylation of the unrefined C4-fraction of the naphtha pyrolysis: after a more than 95 per cent conversion of the buta-1,3-diene also more than 80 per cent of the n-but-1-ene in the C4-fraction is hydroformylated mainly to wanted n-pentanal. Less than 5-10% of the n-but-2-enes and the isobutene in the C4-fraction react under these conditions to oxo-products (2- and 3-methylbutanal). Acetylenic compounds in the C4-fraction are converted quantitatively into products.
Deamination Reactions, 51. - Decomposition of Bicyclohexane-exo-6-diazonium Ions
Kirmse, Wolfgang,Hellwig, Georg
, p. 389 - 392 (2007/10/02)
The nitrous acid deamination of the amine 13, the copper(II)-induced cleavage of the nitrosourea 19, and the thermolysis of the nitrosoamide 20 were used to generate the diazonium ion 7.In contrast to previous work, performed in the presence of base, the neutral to weakly acidic conditions of the present study afforded substantial fractions (30-40percent) of bicyclohex-exo-6-yl products (15).Small quantities of bicyclohex-endo-6-yl (14), bicyclohex-2-yl (25, 26) and 3-cyclohexen-1-yl (27) derivatives were also detected, the latter arising by a 1,3-hydride shift.These results, unprecedented with higher homologs of 7, suggest a largely "classical" bicyclohex-6-yl cation (21) as the initially formed intermediate.Capture of 21 is thought to compete with disrotatory transformation to the cyclohexenyl cation 12. - Keywords: Bicyclohex-6-yl derivatives/ Diazonium ions/ Electrocyclic reactions/ Nucleophilic displacement
Functionalization of Saturated Hydrocarbons. Part 4. The Gif System for Selective Oxidation using Molecular Oxygen
Barton, Derek H. R.,Boivin, Jean,Gastiger, Michel,Morzycki, Jacek,Hay-Motherwell, Robyn S.,et al.
, p. 947 - 956 (2007/10/02)
Various systems for the selective oxidation of saturated hydrocarbons have been developed.These are based on the idea of an iron catalyst which is reduced by electron transfer and oxidized by molecular oxygen simultaneously in the presence of a source of protons.Four modifications of this system (the Gif system) have been devised of which the best (Gif IV) consists of an iron catalyst with metallic zinc as the reductant, acetic acid as the proton source and pyridine as the solvent.At room temperature, using oxygen or air, saturated hydrocarbons are oxidized selectively to ketones in isolated yields superior to those reported for comparable model systems.
Ozonolysis of Symmetrically 1,2-Disubstituted Ethylenes in HCl/Methanol Solutions: Acid Catalyzed Reactions of Primary Cleavage Products
Griesbaum, Karl,Neumeister, Joachim
, p. 2697 - 2706 (2007/10/02)
The ozonolysis of olefins in 1 M anhydrous solutions of hydrogen chloride in methanol at /= 0 deg C was investigated.Upon warm-up of the ozonolysis products, the peroxidic primary fragmentation products were converted into non peroxidic end-products by HCl-catalyzed reactions.Cyclopentene (1a) and cyclohexene (1b), e.g., afforded mixtures of the corresponding α,ω-dialdehydebis(dimethyl acetals) (8), dimethyl α,ω-dicarboxylates (9), and methyl ω-aldehyde dimethyl acetal carboxylates (10).Norbornene (1c) gave a mixture of the correspondingly substituted 1,3-cyclopentane compounds (8c - 10c), phenanthrene (22) gave a mixture of methyl 2'-formyl-2-biphenylcarboxylate (24a), 2,2'-biphenyldicarbaldehyde (24b), and dimethyl 2,2'-biphenyldicarboxylate (24c).A reaction scheme was advanced for the rationalization of the types and the distribution of the products.It was partly substantiated by model reactions.
