Ultrasound-assisted thiocyanation of aromatic and heteroaromatic compounds using ammonium thiocyanate and DDQ

Thiocyanation of various aromatic and heteroaromatic compounds has been achieved in the presence of ammonium thiocyanate (NH(4)SCN) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in methanol solution under ultrasound irradiation. An ultrasonic probe of 24 kHz frequency has been used for this study. Whereas the use of ultrasound increases the rate of reactions compared with reactions at reflux conditions, the electron-donor ability of aromatic nucleus enhances also the rate of reaction.     

Electromembrane extraction through a virtually rotating supported liquid membrane

Electromembrane extraction (EME) of model analytes was carried out using a virtually rotating supported liquid membrane (SLM). The virtual (nonmechanical) rotating of the SLM was achieved using a novel electrode assembly including a central electrode immersed inside the lumen of the SLM and five counter electrodes surrounding the SLM. A particular electronic circuit was designed to distribute the potential among five counter electrodes in a rotating pattern. The effect of the experimental parameters on the recovery of the extraction was investigated for verapamil (VPL), trimipramine (TRP), and clomipramine (CLP) as the model analytes and 2‐ethyl hexanol as the SLM solvent. The results showed that the recovery of the extraction is a function of the angular velocity of the virtual rotation. The best results were obtained at an angular velocity of 1.83 RadS^?1 (or a rotation frequency of 0.29 Hz).The optimization of the parameters gave higher recoveries up to 50% greater than those of a conventional EME method. The rotating also allowed the extraction to be carried out at shorter time (15 min) and lower voltage (200 V) with respect to the conventional extraction. The model analytes were successfully extracted from wastewater and human urine samples with recoveries ranging from 38 to 85%. The RSD of the determinations was in the range of 12.6 to 14.8%.     

Efficient Oxidation of Hantzsch 1,4-Dihydropyridines with Nicotinium Dichromate

A convenient method for the oxidation of various 4-substituted Hantzsch 1,4-dihydropyridines with nicotinium dichromate (NDC) in refluxing acetonitrile is reported. The yields obtained are excellent.     

Photoinduced electron transfer ring opening of α-epoxyketones using 7,7,8,8-tetracyano-p-quinodimethane (TCNQ)

Photoinduced electron transfer ring opening of α-epoxyketones using 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) in methanol and acetic acid solutions resulted in the formation of diastereomeric products, hydroxy ethers and hydroxy esters, respectively. However, the formation of cis-1,3-dioxolanes and cis-spirodioxolanes has been observed on reaction in acetone and cyclohexanone solutions, respectively. The effect of the electron donating character of the substituent influenced the rate of the ring opening. Quantum computational studies explain the mechanism of the addition.     

Voltammetric oxidation of 2-oxo-1,2,3,4-tetrahydropyrimidin-5-carboxamides: substituent effects

Electrochemical oxidation of a series of 20 substituted 2-oxo-1,2,3,4-tetrahydropyrimidin-5-carboxamides (THPMs) in acetonitrile has been studied using voltammetric methods at a glassy carbon electrode to investigate the influence of the substituents on the 4- and 5-positions of the heterocyclic ring. Analysis of the results shows that the electronic nature and steric hindrance of the substituents, especially their orientations toward the heterocyclic ring, determine their effects on the oxidation potential. Analysis of the computational results obtained at the DFT-B3LYP/6-31++G** level of theory suggests a mechanism in which the first electron removal occurs from either the N(1) of the heterocyclic ring or N(17) of the amide substitution. This process is followed by a fast proton removal resulting in the formation of stable allylic and/or benzylic radicals which then undergo further oxidation to the 2-oxo-1,2-dihydropyrimidin-5-carboxamides (DHPMs).     

SELECTIVE AND CONVENIENT OXIDATION OF THIOLS TO DISULFIDES USING n-BUTYLTRIPHENYLPHOSPHONIUM DICHROMATE (Bu n PPh3)2Cr2O7 IN SOLUTION,UNDER SOLVENT-FREE CONDITIONS AND MICROWAVE IRRADIATION

A variety of aliphatic, aromatic, and heteroaromatic thiols were rapidly and cleanly converted to their corresponding disulfides in excellent yields using n-butyltriphenylphosphonium dichromate (BTPPDC) in acetonitrile solution under solvent-free conditions and microwave irradiation. Selective oxidation of thiols in the presence of other oxidizable functional groups, such as alcohol and sulfide, is a noteworthy advantage of this method.     

Aromatization of 1,4-Dihydropyridines Under Mild and Heterogeneous Conditions

A combination of Mg(HSO₄)₂ and NaNO₂ in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of dihydropyridines to their corresponding pyridine derivatives at room temperature with moderate to excellent yields.     

An Efficient Method for the Oxidation of Hantzsch 1,4-Dihydropyridines to their Corresponding Pyridine Derivatives Under Mild and Heterogeneous Conditions

A combination of oxalic acid dihydrate and sodium nitrite in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of dihydropyridines to their corresponding pyridine derivatives at room temperature with excellent yields.