Dynamic and static nature of activated interactions in transition states as elucidated by quantum theory of atoms-in-molecules dual functional analysis: A case of ligand exchange at the N of sulfonylimino-λ3-bromanes

A method to elucidate the dynamic and static natures of the activated interactions in transition states (TSs) is proposed using quantum theory of atoms-in-molecules (QTAIM) dual functional analysis (QTAIM-DFA). The natures are determined for the ligand exchange at the N of sulfonylimino-λ³-bromanes, RBr-*-N(SO₂CF₃)-*-X′R′ (R, R′ = Me or Ph, X′ = Br′ or I′). Asterisks (*) emphasize the presence of bond critical points within the interactions in question. While data from the optimized structures of TSs correspond to the static nature, those from the perturbed and optimized structures represent the dynamic nature. The nature of the interactions in Br-*-N-*-X′ calculated with QTAIM-DFA, using the perturbed structures generated using the normal coordinates for the imaginary frequencies (NIV), was very similar to that in trigonal bipyramidal adduct formation through charge transfer. The results with NIV were precisely the same as those obtained based on intrinsic reaction coordinate (IRC). The high applicability of QTAIM-DFA is demonstrated when analyzing the activated interactions in TSs.     

Stable meso–meso‐Linked 2NH‐Corrole Radical Dimers as a Key Intermediate to Corrole Tape

While oxidation of 5,5′,15,15′‐tetramesityl‐10‐10′‐linked 3NH‐corrole dimer with DDQ gave the corresponding triply linked 2NH‐corrole tape, the use of an equimolar amount of p‐chloranil as a milder oxidant resulted in the formation of a 10‐10′‐linked neutral 2NH‐corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10‐10′‐linked bis‐pyridine‐coordinated Co^III corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.     

Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds

The direct oxidation of unprotected amino alcohols to their corresponding amino carbonyl compounds has often posed serious challenges in organic synthesis and has constrained chemists to adopting an indirect route, such as a protection/deprotection strategy, to attain their goal. Described herein is a highly chemoselective aerobic oxidation of unprotected amino alcohols to their amino carbonyl compounds in which 2‐azaadamantane N‐oxyl (AZADO)/copper catalysis is used. The catalytic system developed leads to the alcohol‐selective oxidation of various unprotected amino alcohols, carrying a primary, secondary, or tertiary amino group, in good to high yield at ambient temperature with exposure to air, thus offering flexibility in the synthesis of nitrogen‐containing compounds.     

Triply Linked Corrole Dimers

The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl₃ afforded meso–meso, β–β, β–β triply linked 2H‐corrole dimers (with two inner NH groups in each corrole unit), which exhibited characteristic ¹H NMR and absorption spectra attributable to their nonaromatic electronic networks. These 2H‐corrole dimers were reduced with NaBH₄ to aromatic 3H‐corrole dimers, which were unstable and easily oxidized back to the 2H‐corrole dimers upon exposure to air. Bis(zinc(II)) complexes of the 2H‐corrole dimers were synthesized and characterized as rare examples of nonaromatic zinc(II) corrole complexes.     

Preparation of poly(p‐oxybenzoyl) crystals using direct polymerization of p‐hydroxybenzoic acid in the presence of boronic anhydrides

Poly(p‐oxybenzoyl) (POB) crystals were prepared by reaction‐induced crystallization during direct polymerization of p‐hydroxybenzoic acid in the presence of boronic anhydrides. Polymerizations were carried out at 300 °C in dibenzyltoluene at a concentration of 1% with three kinds of anhydrides of boronic acid such as 3,4,5‐trifluorophenylboronic acid (TFB), 4‐methoxyphenylboronic acid (MPB) and 4‐biphenylboronic acid (BPB). The POB crystals were formed as precipitates in the solution and the morphology was considerably influenced by both the structure of the boronic anhydride and its concentration (c_B). Needle‐like crystals were firmed in the presence of TFB anhydride (TFBA) at c_Bs of 5 and 10 mol % by the spiral growth of lamellae. Spherical aggregates of slab‐like crystals were formed at c_Bs from 50 to 100 mol %. The polymerization with MPB anhydride and BPB anhydride (BPBA) also yielded the needle‐like crystals at c_Bs of 50 and 5 mol %, respectively. The polymerization with TFBA at lower c_B was favorable to prepare the needle‐like crystal. Molecular weight was also influenced by the structure of the boronic anhydride and c_B. M_n increased generally with c_B and BPBA gave the highest M_n of 14.7 × 10³ at c_B of 100 mol %. The loose packing of the molecules in the crystal caused by the bulkiness of the end‐groups made the polymerization in the crystals more efficiently. Morphology and molecular weight of the POB crystals could be controlled by the chemical structure and the content of boronic anhydride. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Ellipsometry characterization of a-Si:H layers for thin-film solar cells

In order to determine microscopic structures of hydrogenated amorphous silicon (a-Si:H) layers incorporated in a-Si:H-based thin-film solar cells, the spectroscopic ellipsometry (SE) analysis of a-Si:H layers prepared by plasma-enhanced chemical vapor deposition has been performed. In particular, we have characterized the a-Si:H layers by applying a new dielectric function model that allows the evaluation of the SiH₂ bond densities in a-Si:H networks. This model is based on our finding that the a-Si:H dielectric functions in the visible/ultraviolet region vary systematically with the formation of SiH₂-clustered microvoids. We have applied this model to estimate the SiH₂ content in a-Si:H layers fabricated on glass substrates, on which the characterization of the SiH₂ bonding is generally difficult. The validity of the SE analysis has been confirmed from the direct characterization of the SiH_n local structures using infrared ellipsometry.     

Effect of refraction index and thickness of the light guide in the position-sensitive gamma-ray detector using compact PS-PMTs

We constructed a position-sensitive gamma-ray detector consisting of an array of BGO scintillators, a light guide and compact PS-PMTs. The effects of refractive index and thickness of the light guide of a glass plate on the detector performance were investigated. A light guide with higher refractive index and smaller thickness is found better for a good spatial resolution.     

Assembly of a Benzo-Fused Bridged Ketone Scaffold from 1,5,10-Enediynes through One-Pot Ruthenium-Catalyzed Cyclization/Iodine-Mediated Oxidative Ring Expansion

In the presence of a cationic Ru catalyst, 1,6-diynes bearing a terminal styryl moiety underwent [2+2+2] cyclization to produce dehydrobiphenylenes fused with a five-membered ring. Although the cycloadducts were unstable toward purification, their one-pot iodine-mediated ring expansion successfully afforded unprecedented bridged ketone products containing a benzo-fused bicyclo[3.2.1] framework.     

Monolithic silica spin column extraction and simultaneous derivatization of amphetamines and 3,4-methylenedioxyamphetamines in human urine for gas chromatographic-mass spectrometric detection

A simple, sensitive, and specific method with gas chromatography-mass spectrometry was developed for simultaneous extraction and derivatization of amphetamines (APs) and 3,4-methylenedioxyamphetamines (MDAs) in human urine by using a monolithic silica spin column. All the procedures, such as sample loading, washing, and elution were performed by centrifugation. APs and MDAs in urine were adsorbed on the monolithic silica and derivatized with propyl chloroformate in the column. Methamphetamine-d₅ was used as an internal standard. The linear ranges were 0.01-5.0 μg mL⁻¹ for methamphetamine (MA) and 3,4-methylenedioxymethamphetamine (MDMA) and 0.02-5.0 μg mL⁻¹ for amphetamine (AP) and 3,4-methylenedioxyamphetamine (MDA) (coefficient of correlation ≧0.995). The recovery of APs and MDAs in urine was 84-94%, and the relative standard deviation of the intra- and interday reproducibility for urine samples containing 0.1, 1.0, and 4.0 μg mL⁻¹ of APs and MDAs ranged from 1.4% to 13.6%. The lowest detection limit (signal-to-noise ratio ≧ 3) in urine was 5 ng mL⁻¹ for MA and MDMA and 10 ng mL⁻¹ for AP and MDA. The proposed method can be used to perform simultaneous extraction and derivatization on spin columns that have been loaded with a small quantity of solvent by using centrifugation.