97-96-1Relevant academic research and scientific papers
SATURATED HOMOETHER MANUFACTURING METHOD FROM UNSATURATED CARBONYL COMPOUND
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Paragraph 0037-0038; 0040; 0044; 0047-0048, (2020/05/14)
PROBLEM TO BE SOLVED: To provide a method for manufacturing saturated homoether from an unsaturated carboxyl compound at good efficiency. SOLUTION: There is provided a manufacturing method of saturated homoether using an unsaturated carboxyl compound and hydrogen as raw materials, and a catalyst in which a metal is carried on an acidic catalyst carrier. The metal of the catalyst is for example palladium, and the carrier of the catalyst is alumina, silica, silica-alumina, or the like. The unsaturated carbonyl compound as the raw material is 2-butenal, 2-ethyl-2-hexenal, 2-ethyl-2-butenal, 2-hexenal, and manufactured saturated homoether is dibuthylether, bis(2-ethylhexyl)ether, bis(2-ethylbuty)ether, dihexylether, or the like. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPO&INPIT
HIGHLY EFFICIENT METHOD FOR PRODUCING SATURATED HOMOETHER FROM UNSATURATED CARBONYL COMPOUND
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Paragraph 0049; 0051-0052, (2020/07/16)
PROBLEM TO BE SOLVED: To provide a method for efficiently producing a saturated homoether from an unsaturated carbonyl compound. SOLUTION: The method for producing an unsaturated homoether uses an unsaturated carbonyl compound and hydrogen as a raw material, uses a catalyst comprising a metal supported on an acidic catalyst carrier and performs at least once a pressure reduction operation so that a differential pressure from a reaction pressure is 0.01 MPa or more. In the method, the metal of the catalyst is, for example, palladium and the carrier of the catalyst is alumina, silica, silica-alumina or the like. The unsaturated carbonyl compound serving as a raw material is 2-butenal, 2-ethyl-2-hexenal, 2-ethyl-2-butenal, 2-hexenal or the like and the produced saturated homoether is dibutyl ether, bis(2-ethylhexyl)ether, bis(2-ethylbutyl)ether, dihexyl ether or the like. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
Copper promoter effect on acid-base and redox sites of Fe/Al2O3 catalysts and their role in ethanol-acetone mixture conversion
Pinheiro, Antonio Narcisio,Dos Santos, Regina Claudia Rodrigues,Ferreira Dos Santos, Sarah Brenda,Da Silva Júnior, Moacir José,Pinheiro Braga, Tiago,Freire, Valder Nogueira,Valentini, Antoninho
, p. 443 - 458 (2018/02/07)
Active species of copper and iron oxide (Cu-Fe) catalysts supported on alumina were prepared by combining Pechini and wet impregnation methods. The effect of combined acid-base and redox sites of Cu and Fe species on gas-phase ethanol-acetone mixture conversion was investigated. The catalysts were characterized by chemical analyses, XRD, H2-TPR, M?ssbauer spectroscopy, N2 physisorption, CO2-TPD, SEM-EDS, TG/DTA and pyridine adsorption isotherms. N2 adsorption/desorption isotherms and SEM-EDS analysis showed that the addition of copper caused an increase of BET surface area and Cu and Fe oxide dispersion. H2-TPR characterization showed that interactions between Cu and Fe oxides shift the reducibility of Fe3+ species to lower temperature improving the redox properties of the catalyst. The partial reduction of the Cu and Fe oxide species was found to be efficient in inhibiting the side decomposition reactions, improving the catalytic efficiency towards dehydrogenation and hydrogen transfer processes. It was found that acid-base pairs play an important role in the formation of dehydrogenation, dehydration and condensation products from ethanol, while redox sites are decisive for hydrogen transfer reactions with reduction of acetone to isopropanol. H2-TPR and M?ssbauer spectroscopy results for the spent catalysts revealed that the highest catalytic performance of the Cu-FeAl catalysts may be attributed to the good dispersion of the Cu oxide and the site generated by the partial reduction which produces Cu+/Cu0 and Fe2+ active species. A reaction pathway with the participation of the acid-base and redox sites in the formation of products by consecutive dehydrogenation-condensation or dehydrogenation-hydrogenation reactions has been proposed.
Utilization of hexabromoacetone for protection of alcohols and aldehydes and deprotection of acetals, ketals, and oximes under UV irradiation
Chaiseeda, Kittichai,Chantharadet, Ladawan,Chavasiri, Warinthorn
, p. 1305 - 1323 (2017/10/30)
Hexabromoacetone (HBA) was efficiently used for the protection of alcohols and aldehydes and deprotection of benzaldehyde dimethyl acetal, solketal, and other acetals and ketals. In only 10?min, the protection of glycerol yielded 90% of solketal and protection of benzaldehyde gave 95% of benzaldehyde dimethyl acetal. The deprotection of benzaldehyde dimethyl acetal under UV irradiation gave over 90% yield of benzaldehyde within 15?s using only 2.5?mol% of HBA. HBA was also successfully used for deoximation. Solvent was found to play an important role in the efficiency of HBA for these reactions.
Preparation method of key intermediate 2-ethyl butyraldehyde of 2-ethyl butyric acid
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Paragraph 0011-0012, (2017/07/19)
The invention provides a preparation method of a key intermediate, 2-ethyl butyraldehyde, of 2-ethyl butyric acid, wherein the preparation method includes the steps of: adding an ethyl magnesium halide Grignard reagent to a protected alpha-halogenated aldehyde (I) solution, and performing a stirring reaction for 1-10 h at a certain temperature; performing post-treatment and de-protecting the product to obtain the 2-ethyl butyraldehyde. A route in the process in represented as follows. The method has short route and high usage ratio, is low in cost and easy to industrialize, and avoids defects in conventional methods.
BIDENTATE DIPHOSPHORAMIDITES WITH A HOMOPIPERAZINE GROUP AS LIGANDS FOR HYDROFORMYLATION
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Paragraph 0076; 0077, (2017/07/14)
The invention relates to Rh, Ru, Co and Ir complexes comprising bidentate diphosphoramidites as ligands and to the use thereof as catalysts for the hydroformylation of olefins. The invention also relates to a process for preparing an aldehyde from an olefin using the complexes or ligands mentioned.
Acetaldehyde as an ethanol derived bio-building block: An alternative to Guerbet chemistry
Moore, Cameron M.,Staples, Orion,Jenkins, Rhodri W.,Brooks, Ty J.,Semelsberger, Troy A.,Sutton, Andrew D.
, p. 169 - 174 (2017/01/24)
In this work, we describe a highly selective poly-aldol condensation of acetaldehyde, which can readily be obtained via dehydrogenation of ethanol. The process operates under mild temperatures (100°C or less) using commercially available catalysts and exhibits excellent total carbon yield of C4+ products with good selectivity for C6 products. The products derived from the reactions described herein are shown to be candidate drop-in fuel replacements for compression ignition engines and precursors to valuable chemicals.
Method of producing hydrogen of the reaction product and substrate
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Paragraph 0058; 0059, (2017/03/24)
PROBLEM TO BE SOLVED: To provide a new production method requiring no reactor having high stirring power for high-temperature and high-pressure conditions in a gas-liquid catalytic reaction of a liquid phase of a substrate with hydrogen in the presence of a solid catalyst. SOLUTION: Micro or nano bubbles are introduced into a liquid phase consisting of a solvent and a substrate so that a reaction product is produced by gas-liquid contact of the substrate with hydrogen in the presence of the solid catalyst. The substrate is one of organic compounds having an unsaturated carbon bond and secondary and tertiary alcohols. COPYRIGHT: (C)2013,JPOandINPIT
Steric effects and mechanism in the formation of hemi-acetals from aliphatic aldehydes
Daw, Graham,Regan, Andrew C.,Watt, C. Ian F.,Wood, Evan
, p. 1048 - 1057 (2014/01/06)
Some physical properties (pKa, log POW, boiling points) of hexanoic acid 1 (X = COOH) and its seven isomers 2, 3, 4, 5, 6, 7, 8 (X = COOH) are reported. Hexanal 1 (X = CHO) and its seven isomeric aldehydes 2, 3, 4, 5, 6, 7, 8 (X = CHO) are shown to equilibrate, in methanol solution, with their hemi-acetals. Logarithms of equilibrium constants correlate with values of Es for the isomeric C5H11 substituents, and with logs of relative rates for saponification of the corresponding methyl esters with ρ = 0.52, reflecting the reduced steric demand of hydrogen compared to oxygen in the quaternization of ester and aldehydic carbonyl groups. Rates of equilibration have also been measured in buffered methanol. For hexanal, with a 2:1 Et3N:AcOH buffer, the buffer-independent contribution is dominated by the methoxide catalysed pathway. Rates in this medium have been determined for isomers 1, 2, 3, 4, 5, 6, 7, 8 (X = CHO), and their logarithms do not correlate with logarithms of equilibrium constants for hemi-acetal formation or with substituent steric parameters derived from ester formation or saponification, indicating that the steric changes associated with full quaternization of the carbonyl group are not mirrored in the transition structures for hemi-acetal formation. It is suggested that transition states for hemi-acetal formation are relatively early so that steric interactions are effectively those between the nucleophile and ground state conformations of the aldehydes. A comparison of the entropies of hemi-acetal formation with entropies of activation has provided a basis for a suggested transition structure. Comparisons with acid chloride hydrolyses are made. Copyright 2013 John Wiley & Sons, Ltd. Logarithms of equilibrium constants for formation hemi-acetals of hexanal and its seven isomeric aldehydes correlate well with values of Es for the isomeric C5H11 substituents, and with logs of relative rates for saponification of the corresponding methyl esters. Logarithms of rate constants for hemi-acetal formation do not, indicating that the steric changes associated with full quaternization of the carbonyl group are not mirrored in the transition structures for hemi-acetal formation. The reasons for this are discussed. Copyright
Rhodium-catalyzed hydroformylation of olefins: Effect of [bis(2,4-di-tert-butyl) pentaerythritol] diphosphite (alkanox P-24) on the regioselectivity of the reaction
Tijani, Jimoh,El Ali, Bassam
, p. 3492 - 3497 (2008/02/12)
Rhodium (I) associated with [bis(2,4-di-tert-butyl) pentaerythritol] diphosphite (I) as a ligand represents an active catalyst system for highly regioselective hydroformylation of various alkenes. The commercially available bis(2,4-di-tert-butyl)pentaerythritol diphosphite (alkanox P-24) (I), which has been used so far as an antioxidant in the stabilization of polymers, was used as a diphosphite ligand for the selective hydroformylation reaction of olefins. Excellent selectivity towards linear aldehydes and excellent conversions were achieved in the hydroformylation of alkenes. The hydroformylation reaction was applied to various olefinic substrates including the internal alkenes.
