An efficient synthesis of medicinally important indole based triarylmethanes by using propylphosphonic anhydride (T3P®)

Abstract

We have developed an economical and efficient method for the synthesis of medicinally and synthetically important indole-based triarylmethanes by using indoles and benzhydrols in the presence of propylphosphonic anhydride (T3P^®). This methodology is an alternate approach for the C–C bond formation with good to excellent yields. In this T3P-mediated dehydration approach, the by-product is highly soluble in water, so that it can be done at larger scale also. In addition to that this efficient protocol has several advantages such as mild reaction conditions, short reaction time and operational simplicity. We have successfully synthesized pyrrole, imidazothiadiazole and imidazolo pyridine based triarylmethanes also.     

A comparison of selective saturation and selective echo chemical shift imaging techniques

We report on a comparative study of two methods of chemical shift imaging which can be used to selectively image fat and water in vivo. Both methods require a B0 field sufficiently homogenous to resolve the methylene and water spectral lines. One method, called CHESS, uses a chemically selective pulse to saturate the unwanted spectral line. The other method, called SECSI, achieves chemical selectivity by using a soft 180 degree RF pulse in forming a spin echo image. Both methods require that the strength of the B1 RF field be accurately calibrated and homogenous. We show by theoretical analysis that the suppression of unwanted spectral lines is sensitive to the first power of B1 errors in the CHESS method but to the second power of B1 errors in the SECSI method. Experiments with phantoms confirmed the expected non linearity of the SECSI method, and showed superior water suppression factors in phantoms with it. Experiments with a large phantom and a living rabbit showed superior results using the SECSI method, and the best results were obtained using a combination of the two techniques.     

A Projection Method for the Integer Quadratic Knapsack Problem

In this paper we present a new branch and bound algorithm for solving a class of integer quadratic knapsack problems. A previously published algorithm solves the continuous variable subproblems in the branch and bound tree by performing a binary search over the breakpoints of a piecewise linear equation resulting from the Kuhn-Tucker conditions. Here, we first present modifications to a projection method for solving the continuous subproblems. Then we implement the modified projection method in a branch and bound framework and report computational results indicating that the new branch and bound algorithm is superior to the earlier method.     

On the Wigner-Witmer correlation rules for a homonuclear diatomic molecule with the like atoms in identical atomic states

The problem of building the manifold of electronic states of a homonuclear diatomic molecule formed from two like atoms in identical atomic states is readdressed. A conceptually simple approach is presented by invoking a model and all the standard results originally obtained by Wigner and Witmer are reproduced.     

On the convergence of a class of algorithms using linearly independent search directions

Powell has shown that the cyclic coordinate method with exact searches may not converge to a stationary point. In this note we consider a more general class of algorithms for unconstrained minimization, and establish their convergence under the assumption that the objective function has a unique minimum along any line.     

Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 2. Preparation,dissociations, and energetics of 3-hydroxyoxolan-3-yl radical and cation

The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (approximately 56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O[bond]C-2 and C-4[bond]C-5 bond dissociations combined account for approximately 42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C(2)H(3)O and C(2)H(4)O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3(+)) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at approximately 590 and approximately 400 nm.     

Chromatographic and spectroscopic studies of the solvent properties of a new series of room-temperature liquid tetraalkylammonium sulfonates

Fifteen tetraalkylammonium salts of the functionalized sulfonic acids N,N-bis(2-hydroxy- ethyl)-2-aminoethanesulfonic acid, 2-(cyclohexylamino)ethanesulfonic acid and 2-hydroxy-4- morpholinopropanesulfonic acid were synthesized and the eight organic salts that were liquid at room temperature were characterized by physical, spectroscopic and chromatographic methods. All liquid salts were viscous at room temperature but after dilution with a suitable cosolvent could be used as mobile phases in liquid chromatography. For this application, the rapid deterioration of silica-based column packings was more of a deterrent than the physical properties of the salts. The tetraalkylammonium sulfonates had wide liquid ranges and were stable as column packings up to 150–180°C, making them suitable for use in gas chromatography. Their solvent properties were characterized by solvatochromic parameters [E_T(30), π*, α and β] and by thermodynamic parameters determined by gas chromatography. Good agreement was found between the predictions of the two methods. The liquid salts showed strong orientation and solvent hydrogen bond acceptor capacity with weak hydrogen bond donor capacity in spite of the functionalization of the anions. The most probable reason for the weak hydrogen bond donor capacity of the anions is the unavailability of these functional groups for solute interactions owing to their preferential involvement in the formation of anion association complexes. The chemically defined structure, unique solvent properties and wide usable temperature ranges make the tetraalkylammonium sulfonates useful stationary phases for gas chromatography.     

Raman spectroscopy--a new method for the intra-operative assessment of axillary lymph nodes

Sentinel Lymph Node Biopsy has become the standard surgical procedure for the sampling of axillary lymph nodes in breast cancer. Intra operative node assessment is currently not offered to the majority of patients but would allow definitive axillary surgery to take place immediately. This would confer benefits both to the patient and to the healthcare system. Our experimental study aims to demonstrate that a Raman spectroscopy probe device could overcome many of the disadvantages of current intra-operative analysis techniques. 38 axillary lymph nodes, 25 negative and 13 positive from 20 patients undergoing breast surgery for invasive breast cancer were assessed using a commercially available Raman spectroscopy probe. Spectra were assessed using principal component fed linear discriminant analysis trained by the histopathology results. Leave one node out cross validation achieved a sensitivity of up to 92% and a specificity of up to 100% in differentiating between normal and metastatic lymph nodes.