- Method for preparing organic carboxylic ester through combined catalysis of aryl bidentate phosphine ligand
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The invention discloses a method for preparing organic carboxylic ester by combined catalysis of an aryl bidentate phosphine ligand. The method comprises the following steps: under the action of a palladium compound/aryl bidentate phosphine ligand/acidic additive combined catalyst, carrying out a hydrogen esterification reaction on terminal olefin, carbon monoxide and alcohol so as to generate theorganic carboxylic ester with one more carbon than olefin. According to the invention, by adoption of the palladium compound/aryl bidentate phosphine ligand/acidic additive combined catalyst, good catalytic activity and selectivity for the hydrogen esterification reaction of the olefin are achieved, and olefin carbonylation to synthesize organic carboxylic ester can be efficiently catalyzed. Thearyl bidentate phosphine ligand has a rigid skeleton structure of a rigid ligand and the flexibility of a flexible ligand, so the aryl bidentate phosphine ligand has proper flexibility due to the characteristic that the aryl bidentate phosphine ligand is soft and rigid, and a most favorable coordination mode and a stable active structure in space are favorably formed. In addition, the aryl bidentate phosphine ligand has the advantages of high stability, simple and convenient synthesis method and the like; and a novel industrial technology is provided for production of organic carboxylate compounds.
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Paragraph 0038
(2020/05/29)
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- Esterification of Tertiary Amides by Alcohols Through C?N Bond Cleavage over CeO2
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CeO2 has been found to promote ester forming alcoholysis reactions of tertiary amides. The present catalytic system is operationally simple, recyclable, and it does not require additives. The esterification process displays a wide substrate scope (>45 examples; up to 93 % isolated yield). Results of a density functional theory (DFT) study combined with in situ FT-IR observations indicate that the process proceeds through rate limiting addition of a CeO2 lattice oxygen to the carbonyl group of the adsorbed acetamide species with energy barrier of 17.0 kcal/mol. This value matches well with experimental value (17.9 kcal/mol) obtained from analysis of the Arrhenius plot. Further studies by in situ FT-IR and temperature programmed desorption using probe molecules demonstrate that both acidic and basic properties are important, and consequently, CeO2 showed the best performance for the C?N bond cleavage reaction.
- Toyao, Takashi,Nurnobi Rashed, Md.,Morita, Yoshitsugu,Kamachi, Takashi,Hakim Siddiki,Ali, Md. A.,Touchy,Kon, Kenichi,Maeno, Zen,Yoshizawa, Kazunari,Shimizu, Ken-ichi
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p. 449 - 456
(2018/09/11)
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- Cathodic reductive couplings and hydrogenations of alkenes and alkynes catalyzed by the B12 model complex
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The reductive coupling and hydrogenation of alkenes were catalyzed by the B12 model complex, heptamethyl cobyrinate perchlorate (1), in the presence of acid during electrolysis at??0.7?V vs. Ag/AgCl in acetonitrile. Conjugated alkenes showed a good reactivity during electrolysis to form reduced products. The product distributions were dependent on the substituents at the C[dbnd]C bond of the alkenes. ESR spin-trapping experiments using 5,5-dimethylpyrroline N-oxide (DMPO) revealed that the cobalt-hydrogen complex (Co–H complex) should be formed during the electrolysis and it functioned as an intermediate for the alkene reduction. The electrolysis was also applied to an alkyne, such as phenylacetylene, to form 2,3-diphenylbutane (racemic and meso) and ethylbenzene via styrene as reductive coupling and hydrogenated products, respectively.
- Shimakoshi, Hisashi,Luo, Zhongli,Tomita, Kazuya,Hisaeda, Yoshio
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- Ester manufacturing method (by machine translation)
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PROBLEM TO BE SOLVED: To produce an ester compound by transesterification using an inexpensive and low toxic inorganic compound. SOLUTION: Transesterification of an ester compound and an alcohol compound is carried out under the presence of lanthanum nitrate (for example, lanthanum nitrate hexahydrate) and a phosphine compound (for example, tri-n-octylphosphine), thereby obtaining the ester product. For example, transesterification of dimethyl carbonate and benzyl alcohol is carried out under the presence of 1 mol% of lanthanum nitrate hexahydrate, and 2 mol% of tri-n-octylphosphine, thereby obtaining benzyl methylcarbonate at a yield of >99%. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0075; 0076
(2017/02/17)
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- A powerful tool for acid catalyzed organic addition and substitution reactions
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A novel green chemistry tool for acid catalyzed reactions has been developed. The multipurpose tool is based on the ability of dry solid materials to donate protons (H+) to starting materials combined with the simultaneous use of a nucleophile (e.g. NaI). The methods enable the following reactions to be conducted at 20-50 °C: selective addition of iodine or alcohols to more substituted carbon in R2CCH2 systems (R ≠ H), esterification reactions, e.g. free fatty acids with methanol, and at higher temperatures, (60-100 °C): esterification of free fatty acids with hindered alcohols (isopropanol), addition of iodine to CC bonds, opening of oxygen(s) containing heterocyclic rings, selective substitution of primary OH groups to iodine in the presence of other functional groups or secondary alcohol groups, esterification of alcohols with nitriles (R-CN), transesterification of fatty acid triglycerides to biodiesel and selective derivatization of primary hydroxyl groups (-CH2OH) over secondary moieties of sugars without any protection. Most of the reactions were also performed by a re-used Dowex cation exchange resin.
- Turhanen, Petri A.,Veps?l?inen, Jouko J.
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p. 26218 - 26222
(2015/10/20)
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- Lewis Acid Catalyzed Synthesis of α-Trifluoromethyl Esters and Lactones by Electrophilic Trifluoromethylation
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An electrophilic trifluoromethylation of ketene silyl acetals (KSAs) by hypervalent iodine reagents 1 and 2 has been developed. The reaction proceeds under very mild conditions in the presence of a catalytic amount of trimethylsilyl bis(trifluoromethanesulfonyl)imide (up to 2.5 mol %) as a Lewis acid providing a direct access to a variety of secondary, tertiary, and quaternary α-trifluoromethyl esters and lactones in high yield (up to 98%).
- Katayev, Dmitry,Matou?ek, Václav,Koller, Raffael,Togni, Antonio
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supporting information
p. 5898 - 5901
(2015/12/11)
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- PRODUCTION OF ESTERS
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This invention relates to a process for the hydroesterification of olefins in which a hydrocarbon stream containing olefins is reacted with CO and an alcohol in the presence of a catalyst to form a hydrocarbon stream containing esters, wherein the alcohol has more than one carbon atom. The hydroesterification reaction is typically carried out in the presence of a catalyst comprising cobalt and a nitrogen-containing additive such as pyridine and the olefins may be branched. The invention also relates to a process for preparing an alkoxylated ester suitable for use as a surfactant molecule in detergent formulations.
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Page/Page column 22; sheet 9/11
(2008/06/13)
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- Erbium(III) chloride: A very active acylation catalyst
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Erbium(iii) chloride is a powerful catalyst for the acylation of alcohols and phenols. The reaction works well for a large variety of simple and functionalized substrates by using different kinds of acidic anhydrides (Ac 2O, (EtCO)2O, (PriCO)2O, (Bu tCO)2O, and (CF3CO)2), without isomerization of chiral centres. Moreover, the catalyst can be easily recycled and reused without significant loss of activity. CSIRO 2007.
- Dalpozzo, Renato,De Nino, Antonio,Maiuolo, Loredana,Oliverio, Manuela,Procopio, Antonio,Russo, Beatrice,Tocci, Amedeo
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- Scope and mechanistic insights into the use of tetradecyl(trihexyl) phosphonium bistriflimide: A remarkably selective ionic liquid solvent for substitution reactions
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A survey of substitution reactions conducted in a phosphonium bistriflimide ionic liquid is presented. The results demonstrate high selectivity favoring substitution over typically competitive elimination and solvolytic processes even when challenging secondary and tertiary electrophiles are employed. The first reports of Kornblum substitution reactions in an ionic liquid are described that proceed with very high chemoselectivity in favor of nitro over nitroso products and elimi nation side products. The structure-reactivity study indicates that these reactions proceed through a narrow spectrum of pathways ranging from straight SN2 to a preassociation pathway along a saddle point that approaches the SN1 limit. The barrier to the formation of dissociated carbocations is attributed to the structural features of this ionic liquid that favor intervention of the associated nucleophile over dissociation, also preventing cross over to E1 processes. The lack of any basic entity in the phosphonium bistriflimide ionic liquid appears to prevent any potential base-mediated elimination reactions, which makes this a highly selective medium for use in general substitution reactions.
- McNulty, James,Nair, Jerald J.,Cheekoori, Sreedhar,Larichev, Vladimir,Capretta, Alfredo,Robertson
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p. 9314 - 9322
(2007/10/03)
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- ZrOCl2·8H2O: An efficient, cheap and reusable catalyst for the esterification of acrylic acid and other carboxylic acids with equimolar amounts of alcohols
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Esterifications of carboxylic acids with equimolar amount of alcohols could be efficiently catalyzed by ZrOCl2·8H2O. Acrylate esters were obtained in good yields under solvent-free conditions at ambient temperature. The esterification of other carboxylic acids with alcohols also proceeded at ambient temperature or at 50°C to afford esters in high yields. If the esterification was performed in toluene under azeotropic reflux conditions to remove water, both the catalytic activity of ZrOCl 2·8H2O and the rate of esterification could be increased greatly. Furthermore, in the present catalytic system, the esters could be easily separated from the reaction mixtures and the catalyst could be easily recovered and reused.
- Sun, Hong-Bin,Hua, Ruimao,Yin, Yingwu
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p. 263 - 271
(2007/10/03)
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- A mild esterification process in phosphonium salt ionic liquid
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A general, high yielding procedure is described for the esterification of carboxylic acids through carboxylate alkylation in phosphonium salt ionic liquid.
- McNulty, James,Cheekoori, Sreedhar,Nair, Jerald J.,Larichev, Vladimir,Capretta, Alfredo,Robertson, Al J.
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p. 3641 - 3644
(2007/10/03)
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- Erbium(III) triflate as an extremely active acylation catalyst
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Erbium(III) triflate is a powerful catalyst for the acylation of alcohols and phenols. The reaction works well for a large variety of simple and functionalized substrates by using different kinds of acidic anhydrides {Ac 2O, (EtCO)2O, [(CH3)3CO] 2O, Bz2O, and (CF3CO)2O} without isomerisation of chiral centres. Moreover, the catalyst can be easily recycled and reused without significant loss of activity.
- Procopio, Antonio,Dalpozzo, Renato,De Nino, Antonio,Maiuolo, Loredana,Russo, Beatrice,Sindona, Giovanni
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p. 1465 - 1470
(2007/10/03)
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- An improved greener esterification of fatty alcohols using a renewable acid-ionic liquid couple as catalyst-solvent
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We have developed a simple and efficient method for the esterification of various organic acids with C4-C18 alcohols using the 1-octyl-3-methyl- imidazolium tetrafluoroborate-para-toluenesulphonic acid (OMIM/BF 4-PTSA) couple, without organic solvent, either by classic heating or by microwave irradiation. The utilisation of the OMIM/BF4-PTSA couple presents considerable advantages: high yield, low temperature, short reaction time, isolation of the ester by simple decantation, easy reuse of the catalyst couple.
- Nguyen, Hoang-Phuong,Znifeche, Samira,Baboulene, Michel
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p. 2085 - 2093
(2007/10/03)
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- Mg(ClO4)2 as a powerful catalyst for the acylation of alcohols under solvent-free conditions
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A trace amount of magnesium perchlorate (from 0.1 mol% to 1 mol%) is able to promote quantitative acylation, with anhydrides, of a large variety of functionalized alcohols in short times, at room temperature and under solvent-free conditions.
- Bartoli, Giuseppe,Bosco, Marcella,Dalpozzo, Renato,Marcantoni, Enrico,Massaccesi, Massimo,Rinaldi, Samuele,Sambri, Letizia
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- Structure-function correlation in lipase catalysed esterification reactions of short and medium carbon chain length alcohols and acids
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An attempt has been made to correlate the carbon chain lengths of acids and alcohols to the extent of esterification in the Rhizomucor miehei lipase catalyzed esterification reactions involving acids of carbon chain length C2-C5 and alcohols of carbon chain length C1-C8.
- Divakar, Soundar
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p. 1919 - 1922
(2007/10/03)
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- Catalytic esterification of alcohols, carboxylic acids and transesterification reactions with cerium(IV) triflate
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Esterification reactions of alcohols with acetic, chloroacetic, trifluoroacetic, propionic, stearic, and benzoic acids were catalyzed with Ce(OTf)4 in a solvent or under solvent-free conditions with high yields. The formylation and acetylation of primary and secondary alcohols were also easily achieved in ethyl formate and ethyl acetate. A high retention of the configuration was observed in the acetylation and formylation of (-)-menthol.
- Iranpoor, Nasser,Shekarriz, Marzieh
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p. 455 - 458
(2007/10/03)
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- Acetyl Nitrite: a Useful Nitrosating Reagent
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Acetyl nitrite has been prepared, and shown to be a useful reagent for the study of the mechanism of deamination of primary amines.
- Kyte, Andrew B.,Jones-Parry, Richard,Whittaker, David
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