13205-48-6Relevant academic research and scientific papers
Nickel-catalyzed carboxylation of aryl iodides with lithium formate through catalytic CO recycling
Fu, Ming-Chen,Fu, Yao,Shang, Rui,Wu, Ya-Nan
, p. 4067 - 4069 (2020)
A protocol for the Ni-catalyzed carboxylation of aryl iodides with formate has been developed with good functional group compatibility for the synthesis of a variety of aromatic carboxylic acids under mild conditions. The reaction tolerates other functionalities for cross-coupling, such as aryl bromide, aryl chloride, aryl tosylate, and aryl pinacol boronate. The reaction proceeds through a carbonylation process with in situ generated carbon monoxide in the presence of a catalytic amount of acetic anhydride and lithium formate, avoiding the use of gaseous CO. The strategy of CO recycling in catalytic amounts is critical for the success of the reaction.
Benzoin type photoinitiator for free radical polymerization
Esen, Duygu Sevinc,Arsu, Nergis,Da Silva, Jose P.,Jockusch, Steffen,Turro, Nicholas J.
, p. 1865 - 1871 (2013)
Benzoin, a popular photoinitiator for free radical polymerization of vinyl monomers, was improved by introduction of two methyl thioether substituents. This new benzoin derivative showed an about 50 times higher light absorption in the near-UV spectral region and performed better than the unsubstituted benzoin in polymerization experiments in bulk solutions or films of acrylate monomers when low initiator concentrations are used. Laser flash photolysis, low temperature luminescence experiments and photoproduct studies by mass spectrometry suggest that a slow α-cleavage mechanism (kα = 2.2 × 105 s-1) from the electronic triplet state with a quantum yield of 0.1 is the primary photoreaction to generate the initiating free radicals.
Synthesis of phenyl 1-thioglycopyranosiduronic acids using a sonicated Jones oxidation
Allanson, Nigel M.,Liu, Dashan,Chi, Feng,Jain, Rakesh K.,Chen, Anna,Ghosh, Manuka,Hong, Liwu,Sofia, Michael J.
, p. 1889 - 1892 (1998)
Jones reagent selectively oxidizes the primary hydroxyl of 1- thiophenyl glycosides in preference to oxidation at sulfur to give phenyl 1-thioglycopyranosiduronic acids in moderate to excellent yields.
Effects of a sulfur substituent on the behavior and generation mode of aroyloxyl radicals in the photolysis of diaroyl peroxides
Hashimoto, Ji-Ichiro,Segawa, Katsunori,Sakuragi, Hirochika
, p. 261 - 266 (1999)
Continuous light irradiation of bis(p-methylthiobenzoyl) peroxide (p-MeSBPO) at 300 nm in acetonitrile gave only p-methylthiobenzoic acid as a product. On pulsed laser photolysis the absorption spectrum due to intermediate p-methylthiobenzoyloxyl radicals was observed in the region 400-800 nm, and the radical yield was significantly decreased in the presence of 1,3-pentadiene or oxygen as a triplet quencher. The results indicate that p-MeSBPO is decomposed from the excited triplet state and the radicals exclusively undergo hydrogen-atom abstraction from the solvent. The origin of the effect is discussed on the basis of experimental and theoretical results.
Mechanochemical Grignard Reactions with Gaseous CO2 and Sodium Methyl Carbonate**
Pfennig, Victoria S.,Villella, Romina C.,Nikodemus, Julia,Bolm, Carsten
supporting information, (2022/01/22)
A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill and their subsequent reactions with gaseous carbon dioxide (CO2) or sodium methyl carbonate providing aryl and alkyl carboxylic acids in up to 82 % yield is reported. Noteworthy are the short reaction times and the significantly reduced solvent amounts [2.0 equiv. for liquid assisted grinding (LAG) conditions]. Unexpectedly, aryl bromides with methoxy substituents lead to symmetric ketones as major products.
Direct 3-Acylation of Indolizines by Carboxylic Acids for the Practical Synthesis of Red Light-Releasable Caged Carboxylic Acids
Watanabe, Kenji,Terao, Nodoka,Niwa, Takashi,Hosoya, Takamitsu
, p. 11822 - 11834 (2021/07/31)
To enhance the practicality of photouncaging system using 3-acyl-2-methoxyindolizines, direct acylation of indolizines with carboxylic acids was developed using condensation reagents, generally used for peptide coupling. This method allowed for caging a broad range of carboxylic acids with indolizines. The method enabled a facile synthesis of water-soluble caged bioactive carboxylic acids having an intramolecular photosensitizer. The efficient release of carboxylic acids from the synthesized caged compounds upon red light irradiation was confirmed in neutral buffered solutions.
Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
Tiburcio, Estefanía,Greco, Rossella,Mon, Marta,Ballesteros-Soberanas, Jordi,Ferrando-Soria, Jesús,López-Haro, Miguel,Hernández-Garrido, Juan Carlos,Oliver-Meseguer, Judit,Marini, Carlo,Boronat, Mercedes,Armentano, Donatella,Leyva-Pérez, Antonio,Pardo, Emilio
, p. 2581 - 2592 (2021/02/16)
Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal-organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation.
Mirror Symmetry Breaking and Network Formation in Achiral Polycatenars with Thioether Tail
Alaasar, Mohamed,Darweesh, Ahmed F.,Cai, Xiaoqian,Liu, Feng,Tschierske, Carsten
, p. 14921 - 14930 (2021/10/14)
Mirror symmetry breaking in systems composed of achiral molecules is of importance for the design of functional materials for technological applications as well as for the understanding of the mechanisms of spontaneous emergence of chirality. Herein, we report the design and molecular self-assembly of two series of rod-like achiral polycatenar molecules derived from a π-conjugated 5,5’-diphenyl-2,2’-bithiophene core with a fork-like triple alkoxylated end and a variable single alkylthio chain at the other end. In both series of liquid crystalline materials, differing in the chain length at the trialkoxylated end, helical self-assembly of the π-conjugated rods in networks occurs, leading to wide temperature ranges (>200 K) of bicontinuous cubic network phases, in some cases being stable even around ambient temperatures. The achiral bicontinuous cubic Ia (Formula presented.) d phase (gyroid) is replaced upon alkylthio chain elongation by a spontaneous mirror symmetry broken bicontinuous cubic phase (I23) and a chiral isotropic liquid phase (Iso1[*]). Further chain elongation results in removing the I23 phase and the re-appearance of the Ia (Formula presented.) d phase with different pitch lengths. In the second series an additional tetragonal phase separates the two cubic phase types.
Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
Zhao, Bin,Hammond, Gerald B.,Xu, Bo
supporting information, (2021/09/13)
We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
Green synthesis method of aromatic acid
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Paragraph 0048-0122; 0185-0189; 0271-0272, (2020/05/01)
The invention discloses a green synthesis method of aromatic acid. Nickel-catalyzed carbonyl insertion is carried out on aryl iodine in the presence of formate, acid anhydride, a phosphine ligand andan organic solvent by using a nickel catalyst to obtain the aromatic acid. Efficient catalytic conversion is realized by utilizing the cheap nickel catalyst, the reaction conditions are mild, and theoperation is simple.
