A New Tetrahydrofurannulation Via Tandem Radical Cyclization Reaction-Reductive Deoxygenation Sequence

Treatment of bromoketals 2, derived from allyl alcohols 1, with tributyltin chloride, sodium cyanoborohydride and AIBN furnishes the tetrahydrofurannulated products 3 via a 5-exo-trig radical cyclisation reaction followed by reductive cleavage of ketal 4

Rearrangement approaches to sesquiterpenes containing multiple contiguous quaternary carbon atoms. Total synthesis of (+/-)-myltayl-8(12)-ene and (+/-)-6-epijunicedranol

Details of the first total syntheses of the sesquiterpenes myltayl-8(12)-ene and 6-epijunicedran-8-ol are described. The aldehyde 13, obtained by Claisen rearrangement of cyclogeraniol, was transformed into the dienones 12 and 18. Boron trifluoride-diethyl ether mediated cyclization and rearrangement transformed the dienones 12 and 18 into the tricyclic ketones 16 and 17, efficiently creating three and four contiguous quaternary carbon atoms, respectively. Wittig methylenation of 16 furnished (+/-)-myltayl-8(12)-ene (11), whereas reduction of the ketone 17 furnished (+/-)-6-epijunicedranol (23)

A Simple and Convenient One Step Method for the Reductive Deoxygenation of Aryl Ketones to Hydrocarbons

A one step, clean and efficient, conversion of arylaldehydes, ketones and ketals into the corresponding hydrocarbon using ionic hydrogenation conditions employing sodium cyanoborohydride in the presence of two to three equivalents of BF3. OEt(2) is described

First total synthesis of (±)-myltayl-4(12)-ene and single-crystal X-ray structure of exo-12-normyltaylan-4-yl 4-nitrobenzoate

The total synthesis of the unusual sesquiterpene (+/-)-myltayl-4(12)-ene 3 starting from the readily available cyclogeraniol 5 and the single-crystal X-ray structure of the 4-nitrobenzoate 12 of the noralcohol 11 are described

Synthesis and characterization of some new dimesogenic compounds

We have synthesized four different types of dimesogenic compounds involving the cholesteryl moiety as one of the mesogenic constituents, and have investigated their liquid crystalline properties. The molecular structures of these dimesogens have been confirmed by spectral analyses; they exhibit a rich polymorphism, as revealed by optical microscopic and differential scanning calorimetric observations. The studies show that the mesomorphic behaviour is sensitive to the nature of the terminal alkyl chains, and to the structure of the 'second mesogen' that is attached to the cholesteryl unit through a polymethylene spacer

Tuning the fluorescence behavior of liquid crystal molecules containing Schiff-base: Effect of solvent polarity

We report the influence of intermolecular and intramolecular hydrogen bonding on the excited state proton transfer (ESPT) emission behavior of two bent core liquid crystal (BLC) molecules, C 54 H 63 NO 9 (BLC3) and C 60 H 75 NO 9 (BLC4), having a Schiff-base and two long alkyl chains at its two ends. Fluorescence spectra of these BLC molecules dispersed in different solvents show dual emission (at � 365 nm and �425 nm) from the keto and enol tautomers. We observed that the population of these keto and enol tautomers and the corresponding intensities of fluorescence emission are strongly influenced by the solvent polarity. In protic solvents, formation of intermolecular hydrogen bond with the Schiff-base of the BLC molecules is highly favoured than the intramolecular hydrogen bonding. This intermolecular hydrogen bonding drastically reduces the population of the keto tautomers in the excited state, resulting in enhanced enol fluoroscence band along with a weak keto emission band. The observed intensity of the enol fluorescence band is the highest for the most studied polar solvent (methanol). On the other hand, in aprotic solvents, the intramolecular hydrogen bonding is highly favoured, which leads to the formation of keto tautomers in the excited state. Hence, an intense keto emission band is observed for the aprotic solvents along with a weak enol emission band. From the time resolved fluorescence studies we observed a longer life time for the keto band than that for the enol band. This is also related to the delayed emission associated with the vibrational bands resulting from the bulky alkyl chains attached to the ends of the BLC molecules. © 2019 Elsevier B.V

Anisotropic Fast Electrically Switchable Emission from Composites of CsPbBr3 Perovskite Quantum Cuboids in a Nematic Liquid Crystal

Fast electrically switchable anisotropic photoluminescence from a nano-soft composite comprising a nematic liquid crystal (LC) and quantum cuboids of a cesium lead halide perovskite is reported. The magnitude of the anisotropy in emission appears to be dictated by the anisotropy of the LC and the capability of the cuboids to form a linear chain, the latter being evidenced through optical and electron microscopy. Application of an ac electric field of small amplitude and its consequent coupling to the LC director is employed to continuously vary the magnitude of the green emission. By appealing to a two-frequency protocol, the emission could be alternated between the anisotropic limits 40 times faster than with a standard protocol. These studies assume importance to obtain backlight sources having narrow full-width-at-half-maximum (FWHM) and polarized emission for achieving high-quality low-cost LC displays. While conventionally, the light source and the LC are separate entities, the possibility of combining the two functionalities in a single material is highly desirable from the fabrication point of view