122623-81-8Relevant articles and documents
The use of dialkyl carbonates for safe and highly selective alkylations of methylene-active compounds. A process without waste production
Bomben, Andrea,Selva, Maurizio,Tundo, Pietro
, p. 256 - 260 (2007/10/03)
The non-toxic compound dimethyl carbonate (DMC) can be used as a methylating and a methoxycarbonylating agent in place of methyl chloride and phosgene, respectively. We report here that DMC and other dialkyl carbonates (DAlkCs: dimethyl, diethyl and dibenzyl carbonates) allow very selective alkylations of a variety of CH2-acidic compounds. Both arylacetonitriles and alkyl arylacetates react with DAIkCs to yield the mono-C-alkylated derivatives (α-alkyl-α-arylacetonitriles and alkyl α-alkyl-α-arylacetates) with a selectivity of up to 99%, at complete conversion. Likewise, the mono-C-methylation by DMC proceeds selectively also on (aryloxy)acetonitriles and methyl (aryloxy)acetates. The reactions are carried out at temperature of 180-220°C in the presence of weak bases (usually K2CO3); under such conditions, DAlkCs efficiently replace the common and very toxic alkylating agents (dialkyl sulfates and alkyl halides). In addition to the high selectivity obtained and the intrinsic safety of the dialkyl carbonates, the reported reactions give rise to neither organic nor inorganic waste products.
A new synthesis of 2-aryloxypropionic acids derivatives via selective mono-C-methylation of methyl aryloxyacetates and aryloxyacetonitriles with dimethyl carbonate
Bomben, Andrea,Marques, Carlos A.,Selva, Maurizio,Tundo, Pietro
, p. 11573 - 11580 (2007/10/02)
A one-pot procedure for the mono-C-methylation of methyl aryloxyacetates and aryloxyaceto nitriles by dimethyl carbonate (DMC) is reported. The reaction is carried out in an autoclave at high temperatures (180-200°C) and in the presence of a base (K2
Optical resolution of aryloxypropionic acids and their esters by HPLC on cellulose tris-3,5-dimethyl-triphenylcarbamate derivative
Azzolina,Collina,Ghislandi
, p. 1401 - 1416 (2007/10/02)
Chiral chromatographic resolution of a series of antiphlogistic 2- aryloxypropionic acids and their methyl and ethyl esters was performed using a Chiralcel OD column. The CSP selected resolved most of the acids and esters efficiently, the enantiomers being well separated without requiring time consuming analysis. Chromatographic separation of R enriched samples was performed to determine the correct elution order. Using eluting systems such as hexane and 2-propanol, or hexane, 2-propanol and formic acid, the S enantiomer of all acids and esters was always found to elute first. We also considered the role of electron-donating or electron-withdrawing substituents (at the aryloxylic moiety) on the chiral resolution. It was shown that the electronic features of the substituents have more influence on the chiral interactions between the solutes and the CSP than their steric hindrance. Finally we determined, by molecular models, the interaction between CSP and solutes. In this way were able to determine all the potential sites for interactions, which are compatible with the conformations of the compounds and the structure of the stationary phase, and point out those interactions which enable chiral resolution.
