107-93-7Relevant articles and documents
SELECTIVE OXIDATION OF ALCOHOLS BY K2FeO4-Al2O3-CuSO4*5H2O
Kim, Kwan Soo,Song, Yang Heon,Lee, Nam Ho,Hahn, Chi Sun
, p. 2875 - 2878 (1986)
A solid mixture of K2FeO4, Al2O3 and CuSO4*5H2O efficiently oxidized allylic, benzylic, and saturated secondary alcohols to the corresponding aldehydes or ketones but did not oxidize saturated primary alcohols.
Vinylacidic Acid in the Reaction of Aza-Michael with 1-Ethylpyrazole
Arzumanyan, A. M.,Attaryan, H. S.,Danagulyan, G. G.,Khachatryan, H. N.,Shahkhatuni, A. G.
, p. 1488 - 1490 (2020)
Abstract: Commercial vinylacetic acid is a mixture of isomers of but-3-enoic andbut-2-enoic acids. It was shown that but-3-enoic acid undergoes isomerization inthe presence of a catalytic amount of 1-ethylpyrazole. The resulting Z- and E-isomersof but-2-enoic acid enter the aza-Michael reaction with pyrazole. The1H NMR analysis showed that by the end of theexperiment the ratio of unreacted Z- andE-isomers of but-2-enoic acid in thereaction mixture decreased by half (to 3 : 1), which pointed to a higherreactivity of the Z-isomer.
Revisiting the Palladium-Catalyzed Carbonylation of Allyl Alcohol: Mechanistic Insight and Improved Catalytic Efficiency
Jiang, Jianwei,Padmanaban, Sudakar,Yoon, Sungho
, p. 1881 - 1886 (2020)
Although crotonic acid (CA) is in high demand due to its use in various industrial applications, the preparation of CA currently requires a multi-step process from the petrochemical cracking of ethane with a very low overall yield and poor selectivity. An atom economical, one-step, carbonylation of readily accessible allyl alcohol to CA is one of the attractive approaches. In this study, the direct carbonylative transformation of allyl alcohol to CA was analyzed in detail to detect the reaction intermediates and propose a reaction mechanism. Following the reaction mechanism, the process was optimized to synthesize CA via the direct carbonylation of allyl alcohol with improved efficiency and productivity (TON = 420) under mild reaction conditions using Pd-based catalytic systems.
SEVERAL MECHANISMS IN THE ELIMINATION KINETICS OF ω-CHLOROCARBOXYLIC ACIDS IN THE GAS PHASE
Chuchani, Gabriel,Martin, Ignacio,Rotinov, Alexandra,Dominguez, Rosa M.,Perez, Milogrados I.
, p. 133 - 138 (1995)
The kinetics of the gas-phase pyrolysis of ω-chlorocarboxylic acids were examined in a seasoned static reaction vessel and in the presence of at least twice the amount of the free radical inhibitor cyclohexene or toluene.In conformity with the available experimental data on rate determination, these reactions proved to be unimolecular and obeyed a first-order rate law.The presence of the primary chlorine leaving group in Cl(CH2)nCOOH (n=1-4) showed a change in mechanism from intramolecular displacement of the Cl leaving group by the acidic hydrogen of the COOH to anchimeric assistance of the carbonyl COOH to the C-Cl bond polarization in the transition state.This mechanistic consideration is nearly the same for the series of 2-, 3-, and 4-chlorobutyric acids.The chlorine atom at the 2-position of acetic, propionic and butyric acids is dehydrochlorinated through a prevailing reaction path involving a polar five-membered cyclic transition state.
FLAVONOIDS OF Thermopsis alterniflora. CROTONOYLTHERMOPSOSIDE AND CROTONOYLCOSMOSIIN - NEW ACYLATED FLAVONE GLYCOSIDES
Yuldashev, M. P.,Batirov, E. Kh.,Vdovin, A. D.,Malikov, V. M.,Yagudaev, M. R.
, p. 303 - 308 (1989)
From the epigeal part of Thermopsis alterniflora Rgl. et Schmalh. (Fabaceae), in addition to formononetin, ononin, cynaroside, and rothindin, two new acylated flavone glycosides have been isolated and, on the basis of chemical transformations and spectral characteristics, their structures have been established as 4',5,7-trihydroxy-3'-methoxyflavone 7-O-(6"-O-crotonoyl-β-D-glucopyranoside) and 4',5,7-trihydroxyflavone 7-O-(6"-O-crotonoyl-β-D-glucopyranoside).
Straightforward Synthesis of 2-Alkenoic Acids from the Corresponding Saturated Aldehydes
Outurquin, Francis,Paulmier, Claude
, p. 690 - 691 (1989)
2-Alkenoic acids may be prepared in good yields from saturated aldehydes via α-selenenylation with 4-(phenylseleno)morpholine formed in situ, followed by hydrogen peroxide oxidation.The actual oxidizing agent is benzeneperseleninic acid which is formed in the reaction medium.
Effect of the Reaction Products on the Rate of Oxidation of Crotonaldehyde
Fedevich,Levush,Fedevich,Kit
, p. 29 - 32 (2003)
Study of the oxidation of crotonaldehyde revealed an appreciable inhibitory effect of the products on the process. Analysis of the kinetic data obtained over a wide range of reaction conditions (c0 1.5-3.3 M, pO2 1-16 atm, T 293-309 K) showed that the overall oxidation process (with account taken of the inhibitory effect of the products) is described by the equation: WCA = kap* CCA (pO2 )°1.6 (1 + 0.17 Δ cCA τ)-1, where Kap* is the apparent rate constant, and Δ cCAτ is the decrease of the aldehyde concentration by a moment τ.
Ligand-controlled divergent dehydrogenative reactions of carboxylic acids via C–H activation
Wang, Zhen,Hu, Liang,Chekshin, Nikita,Zhuang, Zhe,Qian, Shaoqun,Qiao, Jennifer X.,Yu, Jin-Quan
, p. 1281 - 1285 (2021/12/10)
Dehydrogenative transformations of alkyl chains to alkenes through methylene carbon-hydrogen (C–H) activation remain a substantial challenge. We report two classes of pyridine-pyridone ligands that enable divergent dehydrogenation reactions through palladium-catalyzed b-methylene C–H activation of carboxylic acids, leading to the direct syntheses of a,b-unsaturated carboxylic acids or g-alkylidene butenolides. The directed nature of this pair of reactions allows chemoselective dehydrogenation of carboxylic acids in the presence of other enolizable functionalities such as ketones, providing chemoselectivity that is not possible by means of existing carbonyl desaturation protocols. Product inhibition is overcome through ligand-promoted preferential activation of C(sp3)–H bonds rather than C(sp2)–H bonds or a sequence of dehydrogenation and vinyl C–H alkynylation. The dehydrogenation reaction is compatible with molecular oxygen as the terminal oxidant.
Acrylonitrile Derivatives from Epoxide and Carbon Monoxide Reagents
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Paragraph 0261-0265, (2019/01/15)
The present invention is directed to reactor systems and processes for producing acrylonitrile and acrylonitrile derivatives. In preferred embodiments of the present invention, the processes comprise the following steps: introducing an epoxide reagent and carbon monoxide reagent to at least one reaction vessel through at least one feed stream inlet; contacting the epoxide reagent and carbon monoxide reagent with a carbonylation catalyst to produce a beta-lactone intermediate; polymerizing the beta-lactone intermediate with an initiator in the presence of a metal cation to produce a polylactone product; heating the polylactone product under thermolysis conditions to produce an organic acid product; optionally esterifying the organic acid product to produce one or more ester products; and reacting the organic acid product and/or ester product with an ammonia reagent under ammoxidation conditions to produce an acrylonitrile product.
BIO-BASED METHACRYLIC ACID AND OTHER ALKENOIC-DERIVED MONOMERS VIA CATALYTIC DECARBOXYLATION
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Paragraph 0054-0055; 0056-0057, (2018/04/26)
A novel method for the catalytic selective decarboxylation of a starting material to produce an organic acid is disclosed. According to at least one embodiment, the method may include placing a reaction mixture into a reaction vessel, the reaction mixture including a solvent, a starting material, and a catalyst, subjecting the reaction mixture to a predetermined pressure and temperature, and allowing the reaction to continue for 1-3 hours. The starting material may be at least one of a dicarboxylic acid, a tricarboxylic acid, and an anhydride of a dicarboxylic or tricarboxylic acid. As an exemplary embodiment, itaconic acid may be a starting material and the organic acid may be methacrylic acid. The predetermined temperature may be 250° C. or less, and the reaction pressure may be less than 425 psi. Further, a polymerization inhibitor may be used.
