53448-06-9Relevant academic research and scientific papers
Butadiene hydroformylation to adipaldehyde with Rh-based catalysts: Insights into ligand effects
Yu, Si-min,Snavely, William K.,Chaudhari, Raghunath V.,Subramaniam, Bala
, (2019/12/24)
Rh-catalyzed hydroformylation of butadiene to adipaldehyde is a promising alternative route for producing valuable C6 compounds such as adipic acid and hexamethylenediamine. Fundamental insights into reaction pathways, aimed at enhancing adipaldehyde yield, were obtained from temporal concentration profiles and in situ ReactIR studies of butadiene hydroformylation on Rh complexes at 80 °C and 14 bar syngas (molar CO/H2 = 1) pressure in a batch reactor. Specifically, the effects of operating conditions and eight commercially available ligands on activity and selectivity were systematically investigated. It was found that the adipaldehyde selectivity is independent of the ligand/Rh ratio, rhodium concentration, butadiene concentration and syngas pressure, but significantly dependent on the type of ligand used. For example, while the DIOP ligand provided an adipaldehyde yield of ～40% with butadiene as a substrate, the 6-DPPon ligand gave a maximum adipaldehyde yield of ～93% with 4-pentenal as substrate. Furthermore, the adipaldehyde selectivity correlates well with the natural bite angle of the various ligands. ReactIR studies suggest that the preferential formation of the stable rhodium η3-crotyl complex with the various Rh complexes may be the main reason for the low adipaldehyde selectivity.
Toward the rhodium-catalyzed bis-hydroformylation of 1,3-butadiene to adipic aldehyde
Smith, Stuart E.,Rosendahl, Tobias,Hofmann, Peter
experimental part, p. 3643 - 3651 (2011/09/20)
The effects of the ligand to metal ratio, temperature, syngas pressure, partial pressures of H2 and CO, and new ligand structures have been examined on 12 of the most reasonable products resulting from the rhodium-catalyzed low-pressure hydroformylation of 1,3-butadiene. The selectivity for the desired linear dihydroformylation product, 1,6-hexanedial (adipic aldehyde), is essentially independent of all of these reaction parameters, except for ligand structure. However, the reaction parameters do have a substantial effect on the selectivity for the products, resulting from the branched addition of the rhodium hydride to the carbon-carbon double bond. The optimum reaction parameters and ligand have resulted in a so far unprecedented maximum selectivity of 50% for adipic aldehyde.
Regioselective alkene carbon-carbon bond cleavage to aldehydes and chemoselective alcohol oxidation of allylic alcohols with hydrogen peroxide catalyzed by [cis-Ru(II)(dmp)2(H2O)2] 2+ (dmp = 2,9-dimethylphenanthroline)
Kogan, Vladimir,Quintal, Miriam M.,Neumann, Ronny
, p. 5039 - 5042 (2007/10/03)
(Chemical Equation Presented) [cis-Ru(II)(dmp)2(H 2O)2]2+ (dmp = 2,9-dimethylphenanthroline) was found to be a selective oxidation catalyst using hydrogen peroxide as oxidant. Thus, primary alkenes were very efficiently oxidized via direct carbon-carbon bond cleavage to the corresponding aldehydes as an alternative to ozonolysis. Secondary alkenes were much less reactive, leading to regioselective oxidation of substrates such as 4-vinylcyclohexene and 7-methyl-1,6-octadiene at the terminal position. Primary allylic alcohols were chemoselectively oxidized to the corresponding allylic aldehydes, e.g., geraniol to citral.
Synthesis of oxygen-containing compounds from 1,4-pentadiene
Srednev,Yas'Kina,Moskvichev,Egorova,Shutova,Kozlova
, p. 43 - 47 (2007/10/03)
1,4-Pentadiene oxidation with pinane and cumene hydroperoxides was examined. The application of crude cumene hydroperoxide was shown to yield 90% 1,2-epoxypentene-4 at an oxidant conversion of over 95%. The isomerization of 1,2-epoxypentene-4 in the vapor phase at 290-330°C on lithium phosphate was studied. The rearrangement yielded 2,4-pentadiene-1-ol and unsaturated carbonyl compounds in a nearly 1:1 ratio at an epoxide conversion of 50%. Carbonyl compounds consisted mainly of pentenals with a different double-bond position. The results of the rearrangement show that the epoxide C-O bond heterolysis takes place mainly on the allyl group side.
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.
Asymmetric hydroformylation of conjugated dienes catalyzed by chiral phosphine-phosphite-Rh(I) complex
Horiuchi, Toshihide,Ohta, Tetsuo,Shirakawa, Eiji,Nozaki, Kyoko,Takaya, Hidemasa
, p. 7795 - 7804 (2007/10/03)
Asymmetric hydroformylation of conjugated dienes has been investigated using (R,S)-BINAPHOS-Rh(I) complex as a catalyst [(R,S)-BINAPHOS = (R)-2-(diphenylphosphino)-1,1'-binaphthalen-2'-yl (S)-1,1'-binaphthalene-2,2'-diyl phosphite]. Optically active β,γ-unsaturated aldehydes were obtained in high regio- (78-94%) and enantioselectivities (80-97% ee) from 1-vinylcyclohexene, 4-methyl-1,3-pentadiene, and (E)-1-phenyl-1,3-butadiene. On the other hand, hydroformylation of 1,3-butadiene gave achiral product, (E)- and (Z)-3-pentenal, in up to 95% selectivity. (R)-(E)-2-Methyl-3-pentenal was formed as the major product from both (E)- and (Z)-1,3-pentadiene, but enantioselectivity of the reaction was low. Mechanistic aspects are also discussed.
Asymmetric hydroformylation of conjugated dienes catalysed by [(R)-2-diphenylphosphino-1,1′-dinaphthalen-2′-yl] [(S)-1,1′-dinaphthalene-2,2′-diyl]phosphite-rhodium(I)
Horiuchi, Toshihide,Ohta, Tetsuo,Nozaki, Kyoto,Takaya, Hidemasa
, p. 155 - 156 (2007/10/03)
Asymmetric hydroformylation of conjugated dienes such as vinylcyclohexene, (E)-phenyl-buta-1,3-diene and 4-methyl-penta-1,3-diene using BINAPHOS-RhI complexes as catalysts {(R,S)-BINAPHOS = [(R)-2-diphenylphosphino-1,1′-dinaphthalen-2′-yl] [(S)-1,1′-dinaphthalene-2,2′-diyl]-phosphite} gives optically active β,γ-unsaturated aldehydes in high regio- (81-91%) and enantio-selectivities (84-97% ee).
Selective hydroformylation of open-chain conjugated dienes promoted by mesitylene-solvated rhodium atoms to give β,γ unsaturated monoaldehydes
Bertozzi, Sergio,Campigli, Nedo,Vitulli, Giovanni,Lazzaroni, Raffaello,Salvadori, Piero
, p. 41 - 46 (2007/10/02)
The hydroformylation of 1,3-butadiene, 2-methyl-1,3-butadiene and 1,3-pentadiene using rhodium vapour-mesitylene cocondesates as a catalytic precursor is reported.The reaction gives β,γ-unsaturated monoaldehydes with high chemoselectivity and regioselectivity. η3-Butenyl complexes, derived from the addition of Rh-H species to the conjugated double-bound system, are likely to be intermediates, as suggested by deuterioformylation experiments. Keywords: Rhodium vapour; Hydroformylation; Conjugated dienes; Catalysis; Unsaturated aldehydes
Investigation of Aliphatic Dienes by Chemical Ionization with Nitric Oxide
Budzikiewicz, H.,Blech, St.,Schneider, B.
, p. 1057 - 1060 (2007/10/02)
It is shown that the position of the double bond close to the hydrocarbon end of an aliphatic diene functionalized at C(1) can readily be determined by chemical ionization with NO+.Owing to the low abundance of the ions characteristic for the position of the other double bond, its localization may be difficult.Measurement of the chemical ionization (nitric oxide as reagent gas) spectra of the corresponding epoxides or collision activation studies can help.
