Photochromism of dihydroindolizines Part XIX. Efficient one‐pot solid‐state synthesis,kinetic, and computational studies based on dihydroindolizine photochromes

For the first time, one‐pot solid‐state synthesis of 12 photochromic materials based on photochromic dihydroindolizine system substituted in both fluorene part (region A) and the heterocyclic part (region C) has been established. This method has immense advantages, which are short‐time reaction, high‐yield and low‐yield by‐products, and easily purification and separation processes. In addition, this method will help in getting over the tremendously purification and low‐yield problems faced since the worth‐finding of this family of photochromic materials. The absorption maxima (λ_max) and the half‐lives (t_1/2) of the colored betaines were detected in all cases using multichannel UV/Vis spectrophotometric measurements. The rate constants of the thermal back reaction of the betaines were determined at constant temperature by measuring the decrease in the maximum absorption intensity (λ_max) with time. The half‐lives (t_1/2) and rate constants (k) of betaines under examination were calculated by plotting lnA against time (t). The kinetic measurements could be detected by both spectra scan and time‐dependent decay measurements. Examination of the Arrhenius parameters reveals an underlying compensation between E_a and log A, whereby an increase in E_a is opposed by an increase in log A. The compensation appears in the corresponding Eyring parameters, ΔH^≠ and ΔS^≠; betaine structural changes that lead to lower, more favorable enthalpies of activation engender opposing entropic changes. At the isokinetic temperature T_iso = β, structural changes do not affect the rate constant of a reaction series because the changes of ΔH^≠ are counterbalanced by changes of ΔS^≠. The existence of an isokinetic relationship indicates a common structure of the transition state of all thermal back reaction of betaine under investigation. The computational results suggest that the decoloration reaction is a two‐step mechanism. The first step corresponds to the transoid–cisoid isomerization with an activation barrier of 10.3 kJ mol^?1, and the second step is the ring closure from the cisoid intermediate with a barrier 71.3 kJ mol^?1, which represent the rate determining step for thermal decoloration. The photochemical ring opening of DHIs to betaines is a disrotatory 1,5‐electrocyclic reaction, whereas the thermal ring‐closing occurs in the conrotatory mode. Copyright © 2016 John Wiley & Sons, Ltd.     

X-ray and computational structural study of neutral <Emphasis Type="Italic">bis</Emphasis>(<Emphasis Type="Italic">N,N,N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-tetramethylthiophosphoramidoyl)-methylamine

The structure of bis(N,N,N′,N′-tetramethylthiophosphoramidoyl)-methylamine 1 has been determined by single-crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic system, with a space group P2₁/c, a = 11.836(2) Å, b = 11.659(2) Å, c = 12.796(5) Å and β = 95.28(3)°, V = 1758.3(5) Å³ and Z = 4. The X-ray crystallographic data have been assessed by semi-empirical and ab-initio density functional theory and by Hartree–Fock molecular orbital methods. A comparative study of the results of the different methods is given.     

Synthesis and evaluation of new phosphonated δ-lactam and glutarimide derivatives as angiotensin converting enzyme inhibitors

An efficient synthesis of new γ,δ-insaturated δ-lactam and glutarimide derivatives bearing a phosphonomethyl group from a common allylphosphonate precursor is described. Our approach is based on a two-step procedure involving the preparation of phosphonated-1,5-ketoester and −1,5-diester followed by an amidation–heterocyclization sequence. The first step proceeds via Michael's addition of ethyl acetoacetate and diethyl malonate on an allylphosphonate starting material. The second step consists of a base-promoted intramolecular amidation-cyclization sequence with primary amines, which accounts for the construction of δ-lactams and glutarimide skeletons. We performed the evaluation of angiotensin I-converting enzyme (ACE) inhibition using an in vitro enzyme assay on six new compounds. Five compounds showed potent ACE inhibitory activity, with IC₅₀ values ranging from 0.02 to 0.27 mg/ml. Compared with Captopril, used as a reference drug, two new glutarimide derivatives exhibited higher efficiency ACE inhibition activity.     

New Synthetic Route for Reaching Higher Phase Stabilization in LAMOX-Based Electrolyte for Solid Oxide Fuel Cells

S-substituted La₂Mo₂O₉ were synthesized by a solid-state procedure employing ammonium sulfate (NH₄)₂SO₄ as a sulfur source. The synthesized powders were examined using X-ray diffraction (XRD), thermogravimetric analysis (TGA), infrared, and Raman spectroscopies. The results divulged that the stabilization of the β-La₂Mo₂O₉ polymorph occurred in the interval of sulfur composition 0.1≤y≤0.6. This substitution generates a linear dwindling of the unit cell volume. The decomposition of all substituted samples started above 900 °C with a total weight loss linearly dependent on the sulfur content. Electrical studies confirmed that substituting S⁶⁺ for Mo⁶⁺ suppresses the phase transition of La₂Mo₂O₉ and stabilizes the cubic polymorph down to ambient temperature. It was also remarkable that this substitution caused a decrease in the conductivity, and unfortunately, none of the tested compositions allowed exceeding the conductivity of La₂Mo₂O₉. Infrared and Raman spectra confirmed the presence of the characteristic peaks of sulfates and molybdates groups.