Enolization of acetone in superheated water detected via radical formation

Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied.     

Four‐Component Cyclocondensation of Aminodiazines,Glyoxal, Formaldehyde,and Methanol to Imidazolidines

Four‐component reaction of aminodiazines (2‐aminopyrimidine and 2‐aminopyrazine), glyoxal, formaldehyde, and methanol yields trans‐4,5‐dimetoxy‐1,3‐bis(2‐pyrimidinyl)imidazolidine (5a) and trans‐4,5‐dimetoxy‐1,3‐bis(2‐pyrazinyl)imidazolidine (5b), respectively. Changing methanol to acetonitrile leads to the formation of the corresponding 1,3‐bis(2‐pyrimidinyl) and‐1,3‐bis(2‐pyrazinyl)‐ derivatives of trans‐4,5‐dihydroxyimidazolidine (6). Details of the proposed mechanism are discussed.     

Structures,g-tensors,and hyperfine coupling constants of L-α-alanine radicals in radiation dosimetry: An ab initio molecular dynamics simulation study

Alanine is used as a transfer standard dosimeter for gamma ray and electron beam calibration. An important factor affecting its dosimetric response is humidity which can lead to errors in absorbed dose calculations. Ab initio molecular dynamics calculations were performed to determine the environmental effects on the electron paramagnetic resonance (EPR) parameters of L-α-alanine radicals in acidic and alkaline solutions. A new result, not dissimilar to the closed-shell amino acid molecule alanine, is that the non-zwitterionic form of the alanine radical is the stable form in the gas phase while the zwitterionic neutral alanine radical is not a stable structure in the gas phase. Geometric and EPR parameters of radicals in both gas and solution phases are found to be dependent on hydrogen bonding of water molecules with the polar groups and on dynamic solvation. Calculations on the optimized free radicals in the gas phase revealed that for the neutral radical, hydrogen bonding to water molecules drives a decrease in the magnitudes of g-tensor components g _xx and g _yy without affecting neither g _zz component nor the hyperfine coupling constants (HFCCs). The transfer from the gas to solution phase of the alanine radical anion is accompanied with an increase in the spin density on the carboxylic group's oxygen atoms. However, for the neutral radical, this transfer from gas to solution phase is accompanied with the decrease in the spin density on oxygen atoms. Calculated isotropic HFCCs and g-tensor of all radicals are in good agreement with experiment in both acidic and alkaline solutions.     

Diastereoselective synthesis of novel <Emphasis Type="Italic">N</Emphasis>-substituted pyrrolidine-2-one containing piperazine derivatives

Synthesis of novel hybrid derivatives of two known scaffolds, pyrrolidine-2-one and piperazine, is described. Initially, the Ugi reaction of phenylglyoxal, aromatic amines, coumarin-3-carboxylic acid and isocyanides in methanol resulted in the formation of dihydrochromeno[3,4-c]pyrrole-3,4-diones. The obtained products were then treated with N-alkylpiperazines in dichloromethane to afford the novel N-substituted pyrrolidine-2-one containing piperazine derivatives in satisfactory yields. The proof of the structures was carried out by means of spectroscopic information and X-ray crystallography.     

Evidences of some unusual behaviours of 2‐aminothiazol and 2‐aminobenzothiazol in reactions with formaldehyde and glyoxal

In contrast to the previously reported acid‐catalyzed reaction of 2‐aminothiazole with aqueous formaldehyde in water at 0‐5 °C which afforded N,N′‐bis(2‐thiazolyl)methanediamine ( 4 ), 5,5′‐methylenebis(2‐aminothiazole) ( 5 ) is obtained as the unique product under reflux conditions. Reaction of 2‐aminobenzothiazole with aqueous formaldehyde in acetonitrile at 0‐5 °C or under reflux conditions produces (2‐benzothiazolylamino)methanol ( 6 ) or N,N′‐bis(2‐benzothiazolyl)methanediamine ( 7 ), respectively. Heating monoamine 6 in acetonitrile remarkably yields the symmetric diamine 7 . While cyclocondensation of 2‐aminothiazole with aqueous glyoxal in acetonitrile gives 3,4,8,9‐tetrahydroxy‐7,10‐bis(2‐thiazolyl)‐2,5‐dioxa‐7,10‐diazabicyclo[4.4.0]decane ( 8 ), reaction of 2‐aminobenzothiazole with glyoxal fails to produce similar results; In the presence of aqueous formaldehyde, although the former reaction leads to the formation of 4‐hydroxy‐5‐(thiazolylamino)‐1,3‐bis(2‐thiazolyl)imidazolidine ( 9 ), utilization of 2‐aminobenzothiazole gives 4,5‐dihydroxy‐1,3‐bis(2‐benzothiazolyl)imidazolidine ( 10 ). Condensation of either 6 or 7 with aqueous glyoxal affords compound 10 . Details of the reactions will be discussed in this presentation.     

Growth and characterization of epitaxial Ti3GeC2 thin films on 4H-SiC(0001)

Epitaxial Ti₃GeC₂ thin films were deposited on 4° off-cut 4H-SiC(0001) using magnetron sputtering from high purity Ti, C, and Ge targets. Scanning electron microscopy and helium ion microscopy show that the Ti₃GeC₂ films grow by lateral step-flow with {112?0} faceting on the SiC surface. Using elastic recoil detection analysis, atomic force microscopy, and X-Ray diffraction the films were found to be substoichiometric in Ge with the presence of small Ge particles at the surface of the film.     

Epoxidation of alkenes with molecular oxygen and isobutyraldehyde catalyzed by immobilized vitamin B12 within Al-MCM-41

Vit-B₁₂/ Al-MCM-41 catalyzed successfully the epoxidation either of cis or trans — stilbene with O₂ as oxidant and isobutyraldehyde as co-reductant with 86–98% reactivity and 97–100% selectivity. Other olefins such as norbornene and styrene undergo epoxidation reaction under similar conditions with good to fair selectivity. Details of the reactions will be presented in this article.     

Three-component one-pot synthesis of quinoline–furan conjugates from acetylenedicarboxylate,isocyanide, and 2-chloroquinoline-3-carbaldehyde

We have developed a facile and efficient method for the synthesis of functionalized novel furylquinolines. A variety of quinoline–furan conjugates were obtained via the condensation of 2-chloroquinoline-3-carbaldehyde with acetylenecarboxylates and isocyanides in good to excellent yields.     

Metal ions exchanged montmorillonite as catalyst for alkylation of benzene with 1-dodecene

Summary About 8.5% of benzene was alkylated with 1-dodecene in the presence of Na⁺-montmorillonite. When the reaction was carried out with montmorillonite exchanged with Mn²⁺, Cu²⁺, Ni²⁺, Zn²⁺ and Fe²⁺ ions as catalyst (M²⁺/mont.), 91 to 95% of 1-dodecene was remarkably converted to a mixture of linear monoalkylbenzenes.