Selective Activation of C=C Bond in Sustainable Phenolic Compounds from Lignin via Photooxidation: Experiment and Density Functional Theory Calculations.

Lignocellulosic biomass can be converted to high-value phenolic compounds, such as food additives, antioxidants, fragrances and fine chemicals. We investigated photochemical and heterogeneous photocatalytic oxidation of two isomeric phenolic compounds from lignin, isoeugenol and eugenol, in several nonprotic solvents, for the first time by experiment and the density functional theory (DFT) calculations. Photooxidation was conducted under ambient conditions using air, near-UV light and commercial P25 TiO2 photocatalyst, and the products were determined by TLC, UV-Vis absorption spectroscopy, HPLC-UV and HPLC-MS. Photochemical and photocatalytic oxidation of isoeugenol proceeds via the mild oxidative "dimerization" to produce the lignan dehydrodiisoeugenol (DHDIE), while photooxidation of eugenol does not proceed. The DFT calculations suggest a radical stepwise mechanism for the oxidative "dimerization" of isoeugenol to DHDIE as was calculated for the first time.

A self-assembled, metallo-organic supramolecular frequency doubler.

The dimeric self-assembly program of a new, multidentate ligand with cuprous ions overcomes crystal packing forces, which leads to C(i) symmetry in the solid state, to form a no less than partially C(2)-symmetric structure in solution. The resulting tetranitro-substituted dicopper(i) metallocyclophane displays an exceptionally strong second harmonic frequency response (ß = (3000 ± 600) × 10(-30) esu for a fundamental at 800 nm).

Computational investigation of rearrangements in huisgen cycloadducts of azolium N-dicyanomethanide 1,3-dipoles with alkynes: a mechanistic panoply.

The reaction surfaces leading to rearrangements and ring expansions of azapentalene cycloadducts of imidazolo- and triazolodicyanomethanide 1,3-dipoles with alkynes are studied with the B3LYP DFT method using the 6-31G(d) and 6-311+G(2d,p) basis sets. The surprisingly complex surface involves (1) consecutive but not combined pericyclic steps, a coarctate TS, and pseudopericyclic mechanisms, (2) anchimerically assisted H-atom transfer competing effectively with concerted symmetry-allowed sigmatropic steps, and (3) azolium methanide zwitterions and ketenimines as key intermediates. The azolium methanide is identified as the intermediate detected previously in a variable-temperature NMR experiment that converted the unstable cycloadduct to product imine.

A ceric ammonium nitrate N-dearylation of N-p-anisylazoles applied to pyrazole, triazole, tetrazole, and pentazole rings: release of parent azoles. generation of unstable pentazole, HN5/N5-, in solution.

The reaction of cerium(IV) ammonium nitrate (CAN) with a range of N-(p-anisyl)azoles in acetonitrile or methanol solvents leads to N-dearylation releasing the parent NH-azole and p-benzoquinone in comparable yields. The scope and limitations of the reaction are explored. It was successful with 1-(p-anisyl)pyrazoles, 2-(p-anisyl)-1,2,3-triazoles, 2-(p-anisyl)-2H-tetrazoles, and 1-(p-anisyl)pentazole. The dearylation renders the p-anisyl group as a potentially useful N-protecting group in azole chemistry. The azole released in solution from 1-(p-anisyl)pentazole is unstable HN5, the long-sought parent pentazolic acid. p-Anisylpentazole samples were synthesized with combinations of one, two, and three 15N atoms at all positions of the pentazole ring. The unstable HN5/N5- produced at -40 degrees C did not build up in the solution but degraded to azide ion and nitrogen gas with a short lifetime. The 15N-labeling of the N3- ion obtained from all samples proved unequivocally that it came from the degradation of HN5 (tautomeric forms) and/or its anion N5- in the solution.

Theoretical studies of borazynes and azaborines.

Four isomers of didehydroborazine, B3N3H4, borazyne, and three isomers of azaborine, C4H4BN, are studied by DFT, CCSD, and CCSD(T) computational methods. The singlets of 1,2-borazyne (I) and 1,4-borazyne (IV) have angles about the boron of ca. 150 degrees . In 1,2-azaborine (V), the angles are ca. 140 degrees , while the N angles are ca. 112 degrees except in IV (127 degrees ) and 1,4- azaborine (VII, 120 degrees ). These geometries are almost reversed in the triplets. The 1,3-borazyne (III) shows more bicyclic character than the corresponding m-benzyne, with an N-N distance of 1.7 A. In all cases I was found to be lower in energy than the 2,4-borazyne (II), III, and IV. The order of stability of the azaborines is V > VII > 1,3- azaborine (VI). The nucleus-independent chemical shift (NICS) indicates that all isomers of borazyne are less aromatic than benzene and all isomers of azaborine are about as aromatic as benzene. Time-dependent DFT (TD-DFT) is used to study the excited states of the singlets. The significant structural differences between the singlet and triplet states suggest long phosphoresence lifetimes.

The influence of water on the rates of 1,3-dipolar cycloaddition reactions: trigger points for exponential rate increases in water-organic solvent mixtures. Water-super versus water-normal dipolarophiles.

The nature of the rate enhancements caused by gradually increasing the mole fraction of water in the solvent (from 0 to 1) for the cycloaddition reactions of pyridazinium-dicyanomethanide 1,3-dipole, 2, with the dipolarophiles ethyl vinyl ketone (a water-super dipolarophile) and methyl acrylate (a water-normal dipolarophile) in the organic solvents acetonitrile, acetone, methanol, ethanol, and tert-butyl alcohol at 37 degrees C are explored. In each case as the mole fraction of water surpassed ca. 0.9, exponential rate enhancements were triggered. When methanol replaced water, the rate enhancements were smaller, and no triggering effect was observed. The dramatic rate enhancement triggered for the water-super dipolarophile was significantly reduced as the temperature was raised in the range 29-64 degrees C. The results suggest that a dominant hydrogen-bonding effect operates in water-induced rate enhancements of 1,3-dipolar cycloaddition reactions with water-super dipolarophiles as well as the hydrophobic effect. The hydrogen-bonding effect involves secondary bridging hydrogen bonding from the primary water-solvation shell of the transition state and the growth of structured water clusters. Theoretical calculations strongly support these conclusions.

Consideration of spin states in determining the structure and decomposition of the transition metal pentazoles FeClN5, Fe(N5)2, Fe(H2O)4ClN5, and Fe(NH3)4ClN5.

Optimised geometries and energies have been calculated for the unidentate, bidentate, and ferrocene-like structures of Fe(II) pentazoles of the form MN(5) and M'(N(5))(2), (M = FeCl, M'= Fe) using the UB3LYP DFT method with basis sets up to 6-311+G(3df) in order to study the effect of an unfilled d shell on the stability of the singlet, triplet, and quintet states; the ground state is a quintet and the quintet has a lower barrier to decomposition than the singlet.

Inhibition of the activity of the native gamma-aminobutyric acid A receptor by metabolites of thyroid hormones: correlations with molecular modeling studies.

To characterize the direct effects of thyroid hormones on native gamma-aminobutyric acid(A) (GABA(A)) receptors, rapid (5 s) actions of a series of iodothyronines on muscimol-stimulated uptake of (36)Cl(-) were investigated in synaptoneurosomes prepared from rat brain. The results were correlated with molecular modeling of the active compounds. Dose-response curves for muscimol in the presence of 3,3', 5-L-triiodothyronine (L-T3) indicated a noncompetitive inhibition of muscimol-stimulated (36)Cl(-) uptake by the thyroid hormone. Synaptoneurosomes prepared from cerebellum were less sensitive to L-T3 than those from cerebral cortex, in terms of the potency of the hormone. The overall efficacy approached complete inhibition for both brain regions. Muscimol-stimulated (36)Cl(-) uptake was inhibited differentially by iodothyronine derivatives. One group of compounds with IC(50) values of 18-30 microM included L-thyroxine (L-T4), D-thyroxine (D-T4), 3,3', 5,5'-tetraiodothyroacetic acid (Tetrac), and 3,3', 5-triiodothyroacetic acid (Triac). A second group with values of 75-100 microM included 3,3', 5'-l-triiodothyronine (reverse T3; r-T3), 3,3'-diiodo-L-thyronine (3,3'-l-T2) and 3,5-diiodo-L-thyronine (3,5-D-T2). A final group of inactive compounds with IC(50) values greater than 100 microM included 3',5'-diiodo-L-thyronine (3',5'-l-T2), 3-iodo-L-thyronine (L-T1), 3'-iodo-L-thyronine (3'-L-T1), and L-thyronine (L-T0). Molecular modeling of the active iodothyronines using the Gaussian03 series of programs indicated close correspondences with models of the GABA-inhibitory neurosteroid pregnenolone sulfate (PREGS), suggesting common mechanisms of action at the GABA(A) receptor.

First generation of pentazole (HN5, pentazolic acid), the final azole, and a zinc pentazolate salt in solution: A new N-dearylation of 1-(p-methoxyphenyl) pyrazoles, a 2-(p-methoxyphenyl) tetrazole and application of the methodology to 1-(p-methoxyphenyl) pentazole.

Ceric ammonium nitrate (CAN) in methanol-water gave a new N-dearylation of a series of substituted 1-(p-methoxyphenyl) pyrazoles and a 2-(p-methoxyphenyl)tetrazole producing p-benzoquinone and the parent azole in a mole for mole ratio. Application of this reaction to 1-(p-methoxyphenyl) pentazole at -40 degrees C produced p-benzoquinone. 15N NMR spectra suggest that pentazole, HN5, was also produced and held in solution as N5- with Zn2+ ion. The 15N signal from N5- was -10.0 +/- 2.0 ppm in agreement with calculated values.