Rearrangement of O,O’-bis(2-benzylideneaminophenyl) phenylphosphonite into 1,6,7-triphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-diene

Keeping of O,O’-bis(2-benzylideneaminophenyl) phenylphosphonite in a CCl4 solution for 50 days resulted in its spontaneous rearrangement into 1,6,7-triphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-diene, a representative of spirophosphoranes with P–N bonds.     

A useful scaffold based on acenaphthene exhibiting Cu2+ induced excimer fluorescence and sensing cyanide via Cu2+ displacement approach

A new simple organic scaffold based on acenaphthene 4 was designed and synthesized. The chromogenic and fluorogenic properties of 4 toward different metal ions and anions were investigated in H₂O/MeCN (8:2, v/v) solution. The probe 4 in the presence of Cu²⁺ exhibited strong static excimer emission at 507 nm along with a decrease in monomer emission at ～400 nm ratiometrically, attributed to a complexation through aldimine and amide groups of 4. Additionally, 4 upon interaction with different anions illustrated significant fluorescence enhancement with cyanide. However, interaction of complex, 4-Cu²⁺ with CN^? revealed fluorescence quenching attributed to formation of stable [Cu(CN)_x]^1?x species in the medium. A naked-eye sensitive fluorescent green color of solution was changed to blue. The mechanism of interaction between 4 and Cu²⁺ and sensing of cyanide through Cu²⁺ displacement approach was confirmed by the change in optical behaviors and ¹H NMR and ESI-MS spectral data analysis.     

New regioisomeric naphthol-substituted thiazole based ratiometric fluorescence sensor for Zn2+ with a remarkable red shift in emission spectra

Ratiometric fluorescent chemosensors based on the position of ring annulation of the naphthol–thiazole moiety for quantification of zinc ions in aqueous ethanol were synthesized and investigated. It was found that sensor 3 exhibited a remarkably large red shift of 140 nm in emission upon complexation with Zn²⁺. A TD-B3LYP/6-31G (d,p) calculation was performed to characterize the nature of the fluorescence behavior of sensor 3 upon Zn²⁺ complexation. The combination of experimental and computational analyses provides a more complete understanding of the molecular level origin of these unique photophysical properties of this type of chemosensor.     

Piperidine–iodine a dual system catalyst for synthesis of coumarin bearing pyrrolo[1,2-a]quinoxaline derivatives via a one-pot three-component reaction

The synthesis of 3-(4-alkyl-4,5-dihydropyrrolo[1,2-a]quinoxalin-4-yl)-2H-chromen-2-one derivatives by a three-component reaction of salicylaldehyde, β-keto esters, and 1-(2-aminophenyl)pyrrole using piperidine–iodine as a dual system catalyst is reported. Good yields, mild reaction conditions, and ease of handling are the main aspects of the method. The structural assignments are supported by ¹H NMR, ¹³C NMR, and X-ray crystallography data.     

Chemoselective Route for Synthesis of N‐Aryl‐3‐oxochromeno[2,3‐c]pyrazole‐2(3H)‐carbothioamide Derivatives

A chemoselective route for the synthesis of chromeno[2,3‐c]pyrazole‐2(3H)‐carbothioamide derivatives by a five‐component reaction of salicylaldehyde, malononitrile, NH₂NH₂?H₂O, aryl isothiocyanate, and H₂O in EtOH/AcOH mixture is reported. This new protocol has the advantages of high yields, short reaction times, ease of operation, and simple purification. All structures were confirmed by IR, ¹H‐ and ¹³C‐NMR, and MS analyses. A plausible mechanism for this type of reaction is proposed (Scheme 2).     

π‐Expanded α,β‐Unsaturated Ketones: Synthesis,Optical Properties,and Two‐Photon‐Induced Polymerization

A library of π‐expanded α,β‐unsaturated ketones was designed and synthesized. They were prepared by a combination of Wittig reaction, Sonogashira reaction, and aldol condensation. It was further demonstrated that the double aldol condensation can be performed effectively for highly polarized styrene‐ and diphenylacetylene‐derived aldehydes. The strategic placement of two dialkylamino groups at the periphery of D ‐π‐A‐π‐D molecules resulted in dyes with excellent solubility. These ketones absorb light in the region 400–550 nm. Many of them display strong solvatochromism so that the emission ranges from 530–580 nm in toluene to the near‐IR region in benzonitrile. Ketones based on cyclobutanone as central moieties display very high fluorescence quantum yields in nonpolar solvents, which decrease drastically in polar media. Photophysical studies of these new functional dyes revealed that they possess an enhanced two‐photon absorption cross section when compared with simpler ketone derivatives. Due to strong polarization of the resulting dyes, values of two‐photon absorption cross sections on the level of 200–300 GM at 800 nm were achieved, and thanks to that as well as the presence of the keto group, these new two‐photon initiators display excellent performance so that the operating region is 5–75 mW in some cases.     

Facile and Mild Synthesis and Characterization of Some New Diazo Dyes on the Basis of Schiff Bases in the Presence of Nanocrystalline Magnesium Oxide as a Base Catalyst under Solvent‐free Conditions

In this research, some new diazo dyes including Schiff base have been synthesized by the condensation reaction between ethylenediamine and derivatives of salicylaldehyde containing diazo functional groups in the presence of nanocrystalline magnesium oxide as a solid base catalyst under solvent‐free conditions. Nanocrystalline magnesium oxide has been characterized by XRD, BJH and TEM techniques. The corresponding products have been obtained in excellent yields and high purity. All of the obtained diazo‐Schiff bases are highly colored and can be applicable as useful diazo dyes and characterized by spectroscopy data.     

In-situ copolymerization of aniline with alkyl amine by APS： Kinetics and application

The kinetic study of in-situ eopolymerization of aniline with o- and p-methylaniline by ammonium persulfate （APS） has been carried out. UV-vis spectroscopic method was used to investigate the course of copolymerization. Structural characterization was studied by PT-IR spectral analysis. The electronic spectra of the copolymers poly（aniline-co-p-toluidine） and poly（aniline-co-o- toluidine） show blue shift. The shift has been observed in the bands corresponding to π→π^＊ transition as well as in the exciton transition. The increase in absorbance recorded during the reaction for different concentration of aniline, o- and p-toluidine at various intervals of time of polymerization reaction indicates a growth in the polymer formation. The resulting first-order rate constant was used to calculate the rate of copolymer formation using the rate equation -d[A]/dt = kc^n.     

DC-Pulsed Plasma for Dry Reforming of Methane to Synthesis Gas

The carbon dioxide reforming of methane to synthesis gas under DC-pulsed plasma was investigated. The effects of specific input energy and feed ratio on the product distribution and also feed conversion was studied. At the input energy of about 11 eV/molecule per methane and/or carbon dioxide the feed conversion of 38% for CH₄ and 28% for CO₂ and product selectivity of 74% has been attained for H₂ and CO at feed flow rate of 90 ml/min. The energy consumption in this work displays potential to further study and optimization of the process. The importance of the electron impact reactions in the process was discussed. The results show that by prudent tuning of system variables, the process be able to run in the way of synthesis gas, instead of hydrocarbon production.