122-79-2Relevant articles and documents
Acyl iodides in organic synthesis: I. Reactions with alcohols
Voronkov,Trukhina,Vlasova
, p. 1576 - 1578 (2002)
Reaction of acyl iodides RC(O)I (R = Me, Ph) with alcohols R′OH (R′ = Me, Et, i-Pr, t-Bu, CH2= CHCH2, HC≡CCH2) provides in the corresponding organyl iodides R′I. Unlike that 2-chloroethanol and phenol (R′ = CH 2CH2Cl, Ph) react with RC(O)I in the same way as with acyl chlorides yielding esters RCO2R′. This reaction path occurs partially also with methanol and ethanol.
A sulfonated Schiff base dimethyltin(iv) coordination polymer: Synthesis, characterization and application as a catalyst for ultrasound- or microwave-assisted Baeyer-Villiger oxidation under solvent-free conditions
Martins, Luísa M.D.R.S.,Hazra, Susanta,Guedes Da Silva, M. Fátima C.,Pombeiro, Armando J. L.
, p. 78225 - 78233 (2016)
The synthesis and crystal structure of the new dimethyltin(iv) compound [SnMe2(HL)(CH3OH)]n·(0.5nCH3OH) (1) derived from the Schiff base 2-[(2,3-dihydroxyphenyl)methylideneamino]benzenesulfonic acid (H3L) are described. Despite having six potentially donating centres (one imine nitrogen, two phenoxo and three sulfonate oxygen atoms), the monoprotonated dianionic ligand (HL2-) behaves as an O,O,O-tridentate chelator. Single crystal X-ray diffraction revealed that 1 is a 1D coordination polymer with every tin(iv) ion bound to two methyl groups, a methanol molecule, two Ophenoxo and one μ-Osulfonate atom from HL2-. The coordination polymer 1 was applied as a heterogeneous catalyst for the Baeyer-Villiger oxidation of ketones to esters or lactones, using aqueous hydrogen peroxide as oxidant, under ultrasound (US) or microwave (MW) irradiation and solvent- and additive-free conditions. Overall conversions up to 76/82, 98/93, 93/89, 91/94, 83/90, 68/62 and 81/87% under US/MW irradiations were obtained with 3,3-dimethyl-2-butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, benzophenone and acetophenone, respectively. The catalyst can be recycled up to five cycles without losing appreciable activity.
Chemistry of anti-o,o'-dibenzene
Noh, Taehee,Gan, Hong,Halfon, Sharon,Hrnjez, Bruce J.,Yang, Nien-Chu C.
, p. 7470 - 7482 (1997)
A new and efficient preparation of anti-o,o'-dibenzene 1 has been achieved in three steps from cis-3,5-cyclohexadiene-1,2-diol 25. Utilizing a method for deoxygenation of 1,2-diols developed in our laboratory, anti-tetraol 23 was converted to 1 in 65% yield on a 0.5 g scale; This has allowed us to explore the chemistry of anti-dibenzenes extensively. The kinetics for thermal reversion of 1 to benzene have been studied in three different solvents. The direct photolysis of 1 to benzene has been found to form excited benzene in unit efficiency. This high efficiency of adiabatic photon up-conversion in the singlet manifold is unprecedented. No light was detected in the thermal dissociation of 1 in solution using various sensitizers. The chemiluminescence spectrum from the thermolysis of 1 in the presence of perylene has been recorded and found to correspond to the emission of perylene excimer. Although the efficiency of the chemiluminescent process was very low, it has proven to be one of a very few examples of chemiluminescent reactions from pure hydrocarbons. The possible mechanisms were discussed. Benzene 1,4-endoperoxide 36 was formed during the photolysis of monoperoxide 34 at low temperature. Peroxide 36 underwent a quantitative concerted retrocycloaddition to benzene and singlet oxygen. The half-life of 36 was determined to be 29 min at -30°C.
Baeyer-Villiger oxidation of ketones with a silica-supported peracid in supercritical carbon dioxide under flow conditions
Mello, Rossella,Olmos, Andrea,Parra-Carbonell, Javier,Gonzalez-Nunez, Maria Elena,Asensio, Gregorio
, p. 994 - 999 (2009)
[2-Percarboxyethyl]-functionalized silica reacts with ketones in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions to yield the corresponding esters and lactones. The solid reagent can be easily recycled through treatment with 70% hydrogen peroxide in the presence of an acid at 0°C. This procedure not only simplifies the isolation of the reaction products, but has the advantage of using only water and carbon dioxide as solvents under mild conditions.
-
Laurence et al.
, p. 353 (1977)
-
Platinum and palladium complexes containing cationic ligands as catalysts for arene H/D exchange and oxidation
Emmert, Marion H.,Gary, J. Brannon,Villalobos, Janette M.,Sanford, Melanie S.
, p. 5884 - 5886 (2010)
Cationic catalysts in HD: Palladium(II) and platinum(II) complexes of pyridinium-substituted bipyridine ligands are highly active and stable catalysts for H/D exchange and oxidation of aromatic C-H bonds (TONs up to 3200, TOFs up to 0.1 s-1; se
Enhanced shape selective catalysis of mixed cyclic ketones in aerobic Baeyer-Villiger oxidation with magnetic Cu-Fe3O4 supported mesoporous silica microspheres
Zheng, Chunming,Chang, Shubin,Yang, Chuanwu,Lian, Dongying,Ma, Chao,Zhang, Chunrong,Fan, Xiangrui,Xu, Shichao,Sun, Xiaohong
, p. 2608 - 2616 (2018)
Various strategies have been developed to improve the conversion for the Baeyer-Villiger oxidation. However, the catalytic effects of the Baeyer-Villiger oxidation for the mixed ketones are rarely reported, though it is also important for the natural and industrial separation processes. In this report, magnetite Cu modified Fe3O4 supported mesoporous silica microspheres (Cu-Fe3O4@mSiO2) have been successfully synthesized by two step direct hydrothermal method (DHT). Over 99% of cyclohexanone conversion was obtained with mild air oxidation and benzaldehyde as sacrificing agent over Cu-Fe3O4@mSiO2. The catalytic system also shows higher conversion rates for small molecular ketones in the mixed ketone reactants, which was attributed to the enhanced mass transfer effect and Fe-Cu composite active sites in the magnetite mesoporous silica microspheres. The catalyst could be recycled for four times with similar catalytic performance, which shows enhanced shape selectivity in aerobic Baeyer-Villiger oxidations for mixed cyclic ketones.
Methyl formate as a carbonylating agent for the catalytic conversion of phenol to methyl phenyl carbonate
Yalfani, Mohammad S.,Lolli, Giulio,Wolf, Aurel,Mleczko, Leslaw,Mueller, Thomas E.,Leitner, Walter
, p. 1146 - 1149 (2013)
Methyl formate was used as a green and efficient carbonylating agent in the synthesis of methyl phenyl carbonate from phenol. Methyl formate showed better performance compared to toxic CO gas and the ability to produce other useful carbonylated products, e.g., dimethyl carbonate and dimethyl oxalate.
Reactivity of dehydrometallophthalocyanines and - Porphyrazines
Vagin, Sergei I.,Frickenschmidt, Antje,Kammerer, Bernd,Hanack, Michael
, p. 985 - 991 (2007)
The zinc dehydrophthalocyanine 2 and zinc dehydrobenzoporhyrazine 8a were generated from the 1N-aminobenzotriazole-annulated zinc phtalocyanine 1 and zinc benzoporhyrazine 8, respectively, by oxidation with Pb(OAc)4 in different solvents, for example, diethyl ether, tetrahydrofuran, acetic acid, and benzene. The reactivity of 2 and 8a was studied in detail. These species not only easily undergo Diels-Alder additions with dienes, but also the used solvents can be added. Among the addition products with solvents ethoxy-, acetoxy-, acetoxybutyloxy-substituted and barrelen-fused phthalocyanines and benzoporpyrazines were isolated. No products resulting from the dimerization of two denydro species were observed either for 2 or 8a. Analysis of the reaction products in comparison with those obtained by oxidation of 1-aminobenzotriazole 15 under similar conditions proves a higher reactivity (electrophilicity) of the dehydro-PcZn 2 and dehydro-PzZn 8a in comparison with unsubstituted benzyne towards the solvents used, such as diethyl ether and benzene.
Mechanism of the palladium-catalyzed arene C-H acetoxylation: A comparison of catalysts and ligand effects
Cook, Amanda K.,Sanford, Melanie S.
, p. 3109 - 3118 (2015)
This article describes detailed mechanistic studies focused on elucidating the impact of pyridine ligands on the Pd-catalyzed C-H acetoxylation of benzene. Three different catalysts, Pd(OAc)2, Pd(OAc)2/pyridine (1:1), and Pd(OAc)2/pyridine (1:2), are compared using a combination of mechanistic tools, including rate and order studies, Hammett analysis, detailed characterization of catalyst resting states, and isotope effects. The data from these experiments implicate C-H activation as the rate-limiting step in all cases. The major difference between the three catalysts is proposed to be the resting state of Pd. Under the reaction conditions, Pd(OAc)2 rests as an acetate bridged dimer, while the Pd(OAc)2/pyridine (1:2) catalyst rests as the monomer (pyridine)2Pd(OAc)2. In contrast, a variety of experiments suggest that the highly active catalyst generated from the 1:1 combination of Pd(OAc)2 and pyridine rests as the dimeric structure [(pyridine)Pd(OAc)2]2.
-
Friess
, p. 14 (1949)
-
Chemistry of diamino-ligated methylpalladium(II) alkoxides and aryloxides (Part II): Methoxide formation and carbonylation reactions
Kapteijn, Gerardus M.,Dervisi, Athanasia,Verhoef, Michel J.,Van Den Broek, M.A. Frederik H.,Grove, David M.,Van Koten, Gerard
, p. 123 - 131 (1996)
Reaction of N-ligated methylpalladium(II) alkoxide and aryloxide complexes [Pd(Me)(OR)(N ~ N)] (R = Ph, CH(CF3)2; N ~ N = tmeda (N,N,N′,N′-tetramethylethylenediamine) or bpy (2,2′-bipyridyl)) with carbon monoxide produces the corresponding methylesters in high yields. The insertion takes place either into the Pd-Me bond (aryloxide complexes) or into the Pd-OR bond (alkoxide complexes). Methylpalladium(II) methoxide complexes [Pd(Me)(OMe)(N ~ N)] (N ~ N = tmeda, bpy) have been generated in situ by aryloxide- or alkoxide-methanol exchange reactions for which the equilibrium constants have been determined. The bpy-ligated methylpalladium methoxide complex undergoes insertion of CO producing either a methylpalladium methoxycarbonyl complex [Pd(Me)(CO2Me)(bpy)] (at -60°C) or an acylpalladium methoxycarbonyl complex [Pd(COMe)(CO2Me)(bpy)] (at -25°C); both carbonylated species could be isolated and characterized at low temperature.
Study on the effect of di- and trifluoromethyl groups on the Baeyer-Villiger reaction
Kitazume, Tomoya,Kataoka, Junichi
, p. 157 - 158 (1996)
Case studies of the Baeyer-Villiger reaction applied to di-and trifluoromethylketone derivatives and the effect of the fluoromethyl groups on the Baeyer-Villiger reaction, are described.
O-arylation of carboxylic acids using (phenyl)[2-(trimethylsilyl)phenyl] iodonium triflate as a precursor of arynes
Xue, Jian,Huang, Xian
, p. 2179 - 2185 (2007)
Using (phenyl)[2-(trimethylsilyl)phenyl]iodonium triflate as a precursor of arynes, Larock's method for O-arylation of carboxylic acids and arynes was developed. A variety of acids including simple aliphatic carboxylic acids, aromatic carboxylic acids, allenoic acids, and p-toluenesulfonic acid under mild reaction conditions could generate the aryl esters. Copyright Taylor & Francis Group, LLC.
Versatile mesoporous carbonaceous materials for acid catalysis
Budarin, Vitaly L.,Clark, James H.,Luque, Rafael,Macquarrie, Duncan J.
, p. 634 - 636 (2007)
Starbon mesoporous materials were synthesized after pyrolysis of expanded starch and subsequently functionalised with sulfonated groups, providing highly active and reusable materials in various acid catalysed reactions. The Royal Society of Chemistry.
Efficient Baeyer–Villiger Oxidation Catalysed by Silver Nanoparticles Stabilized on Modified Montmorillonite
Borah, Subrat Jyoti,Das, Diganta Kumar
, p. 3669 - 3677 (2018)
Abstract: Silver nanoparticles supported on modified montmorillonite clay (Ag-NPs@mont), were utilized as catalyst for the Baeyer–Villiger oxidation of various ketones with hydrogen peroxide as an oxidant under solvent free condition at room temperature. The modification of Montmorillonite K10 clay was carried out with HCl under controlled conditions for generating a high surface area porous matrix which acts as support for the in situ generation of Silver nanoparticles. The synthesized nanocomposite material was characterized by UV–Visible spectroscopy, powder XRD, SEM-EDX, TEM and N2 adsorption–desorption analysis. The catalyst can be recycled and reused several times without significant loss of their catalytic activity. Graphical Abstract: [Figure not available: see fulltext.].
Reaction of carboxylic acid esters with phenolates in oil-in-water microemulsions based on cetyltrimethylammonium bromide
Mirgorodskaya,Valeeva,Kudryavtseva,Vylegzhanina,Zuev
, p. 590 - 595 (2006)
A kinetic study of reactions of carboxylic acid esters with phenols activated with alkalis or amines in microemulsions based on cationic surfactants showed that the phenolates formed upon activation exhibit different nucleophilicity depending on the value of the negative charge on the oxygen atom, which is determined by the properties of the phenol, ionizing agent, and solvent. Pleiades Publishing, Inc., 2006.
Vinyl Phosphonic Acid Functionalized Silica Polymer Nanocomposites for the Acylation of Phenol
Amit, Dubey,Verma, Savita
, p. 724 - 733 (2022/01/13)
Abstract: In order to overcome the corrosive problems of homogeneous vinyl phosphonic acid (VPA), ordered mesoporous silica (SBA-15) is functionalized with VPA via in situ radical polymerization method to achieve SBA/VPA nanocomposites with different amou
Preparation method of O-methoxyacetophenone
-
Paragraph 0027-0028, (2021/02/10)
The invention relates to a preparation method of o-methoxyacetophenone. A composite catalyst containing heteropolyacid and Lewis acid is adopted and can effectively catalyze the reaction of dimethyl ether and o-hydroxyacetophenone so that the use of dimethyl sulfate and other highly toxic substances as reaction reagents is avoided, the production cost is lowered, the discharge of highly toxic substances is reduced, and the process is enabled to be greener and more environment-friendly.
Development of pH-activatable fluorescent probes for rapid visualization of metastatic tumours and fluorescence-guided surgeryviatopical spraying
Cao, Wenwen,Li, Xiaoxin,Wu, Peng,Xiong, Hu
supporting information, p. 10636 - 10639 (2021/10/19)
A series of pH-activatable aza-BODIPY-based fluorescent probes were developed for rapid cancer visualization and real-time fluorescence-guided surgery by harnessing topical spraying. These probes exhibited good water-solubility, a tunable pKafrom 5.0 to 7.9, and stable intense NIR emission at ~725 nm under acidic conditions.AzaB5with a pKavalue of 6.7 was able to rapidly and clearly visualize pulmonary and abdominal metastatic tumours including tiny metastases less than 2 mmviatopical spraying, further improving intraoperative fluorescence-guided resection. We believe thatAzaB5is promising as a powerful tool to rapidly delineate a broad range of malignancies and assist surgical tumour resection.