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.
Direct Synthesis of trans-1,4-Diacetoxycyclohexa-2,5-diene by Electrochemical Reduction of r-1,t-4-Diacetoxy-t-2,c-3-dibromocyclohex-5-ene
Kelebekli, Latif,Demir, Uemit,Kara, Yunus
, p. 402 - 403 (1997)
Electrochemical reduction of r-1,t-4-diacetoxy-t-2,c-3-dibromocyclohex-5-ene 1 gives only trans-1,4-diacetoxycyclohexa-2,5-diene 2 in good yield while the commonly used Zn reduction gives a product mixture containing 2 and acetoxybenzene 3 derived from acetoxy elimination.
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.
Acyl iodides in organic synthesis: II. Reactions with acyclic and cyclic ethers
Voronkov,Trukhina,Vlasova
, p. 1579 - 1581 (2002)
Reaction of acyl iodides RCOI (R = Me, Ph) was studied with acyclic and cyclic ethers (Et2O, MeCHCH2(O), ClCH2CHCH 2(O), THF, O(CH2CH2)2O, EtOCH 2CH2OH, EtOCH=CH2, PhOEt]. The reaction occurred with the rupture of one or two CO bonds furnishing the corresponding iodides and esters.
BIPHASE AND TRIPHASE CATALYSIS. ARSONATED POLYSTYRENES AS CATALYSTS IN THE BAEYER-VILLIGER OXIDATION OF KETONES BY AQUEOUS HYDROGEN PEROXIDE.
Jacobson,Mares,Zambri
, p. 6938 - 6946 (1979)
Arsonated polystyrene resins, prepared by a novel procedure, proved to be versatile catalysts for the Baeyer-Villiger oxidation of ketones by hydrogen peroxide. The insoluble beads of the catalyst can be quantitatively separated from the reaction mixture and recycled. Extensive hydrolysis of the lactone and ester products is prevented. In solvents miscible with aqueous hydrogen peroxide (biphase system), the catalysts facilitate oxidation of medium size cycloalkanones (C//4-C//7) and their alkyl and aryl derivatives, steroid ketones, and branched-chain aliphatic ketones. Larger size cycloalkanones, acetophenone, and straight-chain aliphatic ketones react very slowly or not at all. The arsonated polystyrene beads are effective catalysts and phase transfer agents in solvents immiscible with aqueous hydrogen peroxide. This represents the first example of triphase catalysis in oxidations by hydrogen peroxide.
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
Baeyer-Villiger oxidation with potassium peroxomonosulfate supported on acidic silica gel
Gonzalez-Nunez, Maria E.,Mello, Rossella,Olmos, Andrea,Asensio, Gregorio
, p. 10879 - 10882 (2005)
Potassium peroxomonosulfate deposited onto silica SiO2· KHSO5 efficiently reacts with ketones in dichloromethane at room temperature to give the corresponding esters or lactones in quantitative yields. This method avoids hydrolysis of the reaction products. The Baeyer-Villiger reaction is catalyzed by potassium hydrogensulfate present in the supported reagent.
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.
