Synthesis and anion binding of 2-arylazo-meso-octamethylcalix[4]pyrroles

2-Arylazo-5,5,10,10,15,15,20,20-octamethylcalix[4]pyrroles (azo-OMCPs) have been synthesised by the reaction of calix[4]pyrrole with aryldiazonium chloride in 15–45% yields. The solution-state binding studies of the synthesised hosts were investigated by absorption spectroscopy and ¹H NMR in DMSO and CDCl₃, respectively. These receptors, appended with electron-donating and electron-withdrawing groups, displayed enhanced affinity and selectivity for fluoride anion. Well-defined colour change in the visible region of the spectrum was observed upon addition of fluoride ion in DMSO solution of azo-OMCPs. Detailed NMR studies in CDCl₃ revealed that azo-OMCPs with nitro and chloro groups have higher binding affinity for fluoride ion.

     

Association reaction between SiH3 and H2O2: a computational study of the reaction mechanism and kinetics

The association reaction between silyl radical (SiH₃) and H₂O₂ has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH₃–H₂O₂ association in the temperature range 250–600 K, k(T) = 6.89 × 10^?13 T ^?0.163exp(?0.22/RT) cm³ molecule^?1 s^?1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH₂(OH)₂ + H, is the major decomposition channel followed by secondary dissociation leading to SiO.     

Synthesis of (R)‐Japonilure and (4R,9Z)‐9‐Octadecen‐4‐olide,Pheromones of the Japanese Beetle and Currant Stem Girdler

Asymmetric total synthesis of the sex pheromones of Japanese beetle and currant stem girdler, (R)‐japonilure (1) and (4R,9Z)‐9‐octadecen‐4‐olide (2), has been achieved.     

A Simple and Short Synthesis of Z-6-Heneicosen-11-One and Z-1,6-Heneicosen-11-One,The Sex Pheromones of Douglas-Fir Tussock Moth

Z-6-Heneicosen-11-one (1) and Z-1,6-Heneicosen-11-one (2) are the sex pheromones of the Douglas-Fir Tussock moth, ‘Orgyia Pseudo Sugata’, isolated^1,2 in 1975 and 1978 respectively. In contrast with other lepidopterous pheromones, which are unsaturated C₁₂-C₁₄ primary alcohols or acetates, these were found to be C₂₁ ketones. The Douglas-Fir Tussock moth is a severe defoliator of the Fir forest; consequently, considerable interest attends the synthesis of these two pheromones. A number of syntheses of these two pheromones have been reported3 amongst which is one of our synthesis using N,N-dimethyl acetone 4 hydrazone as key intermediate.     

Kinetic Studies on Interaction of Platinum(II) Complexes with an ‘S’ Containing Ligand in Aqueous Medium

The kinetics of the substitution reactions of [Pt(dach)(H₂O)₂]²⁺ and [Pt(en)(H₂O)₂]²⁺ (where ‘dach’ and ‘en’ are cis-1,2-diaminocyclohexane and ethylenediamine, respectively) with excess N,N′-diethylthiourea have been studied in aqueous solution by UV–Vis spectrophotometry. The effect of different N–N spectator ligands on the reactivity of platinum(II) complexes was investigated by studying the water lability of the reactant complexes. The kinetic study has been substantiated by product isolation, IR, NMR and ESI-MS spectral analysis and DFT calculations. The reactions follow normal square-planar substitution mainly in an associative way. Rate parameters have been evaluated under different conditions. The substitution rates of the complexes studied can be tuned through the nature of the N–N chelates, which is important in the development of new active compounds for cancer therapy.     

Mechanism of structure formation of microbial cellulose during nascent stage

The structure of microbial cellulose (MC) produced by Acetobacter xylinum was studied in presence of Fluorescent Brightener, Direct Blue 1, 14, 15, 53, Direct Red 28, 75 and 79, as probe. X-ray diffraction pattern of the product showed that it was a crystalline complex of dye and cellulose. The product has the structure in which the monomolecular layer of the dye molecule is included between the cellulose sheets corresponding to the ( $ 1\bar{1}0 $ ) planes of microbial cellulose. As a result of dye inclusion, d-spacing of lower angle plane (100) of products becomes 8.0–8.8 Å instead of 6.1 Å of MC. The d-spacing for the higher angle plane must be (010) plane due to stronger van der Waals forces between the pyranose rings which reduced 5.3 Å space of (110) plane of MC to 3.9–4.5 Å in the product. However, cellulose regenerated from FB, DR28 products was cellulose I and IV, respectively, and that from each DB1, 14, 15, 53, DR75 and 79 products was cellulose II. Solid state ¹³C NMR and deuteration-IR showed the product was non-crystalline which was contrasted to X-ray results. The regenerated celluloses were cellulose I_β, IV_I and II, respectively. Thus the structure of the product depends on the characteristics of dye which affects the conformation of cellulose at the nascent stage by the direct interaction with cellulose chains. The different regenerated celluloses as well as different fine structure in the same cellulose allomorph were produced depending mainly on number and position of the sulfonate groups in the dye.     

Novel betaines/mesoionic compounds via a simple and convenient MCR in aqueous micellar system: synthesis of thiazolo[2,3-a]isoquinolin-4-ium derivatives

An inexpensive one-pot green methodology has been developed for the synthesis of thiazolo[2,3-a]isoquinolin-4-ium derivatives by the reaction of different derivatives of isoquinoline and 2-bromoacetophenone/bromoacetonitrile with benzoyl isothiocyanate in aqueous micellar medium.     

O-Aryloxime ether analogues as novel and efficient ligands for palladium-catalyzed Suzuki–Miyaura coupling in water

O-Aryloxime ether analogues L1–L3 were studied as ligands in palladium-catalyzed Suzuki–Miyaura cross-coupling reaction of aryl bromides and aryl boronic acids in water at room temperature. Reaction conditions for the cross-coupling were optimized using PdCl₂ and Pd(OAc)₂ under aerobic condition. From the three electronically diverse O-aryloxime ether ligands studied herein, the use of 1-phenyl-ethanone O-(4-chloro-phenyl)-oximeL2 exhibits the best catalytic system in the presence of K₂CO₃ as the base and TBAB as the promoter.     

Facile conversion of para-benzoquinones to para-alkoxyphenols with primary/secondary alcohols and amberlyst-15: a process showing novel reducing property of such alcohols

A new efficient methodology has been developed for the synthesis of para-alkoxyphenols, an important group of anti-melanoma compounds, by heating alcoholic solutions of para-benzoquinones in the presence of amberlyst-15. The most notable feature here is the behaviour of the used primary or secondary alcohol as an effective reducing agent.