abstract
Bis(4,5-dimethyl-2-pyridyl)-, bis(5-methyl-2-pyridyl)- and bis(4-methyl-2-pyridyl) diselenide have been synthesized directly from 3,4-lutidine (1a), 3-picoline (1b) and 4-picoline (1c) respectively via BF3 aided lithiation reaction. The lithiation of 3,4-lutidinium-, 3- and 4-picolinium-BF3 adduct (2a/2b/2c) gives the corresponding carbanion (3a/3b/3c) which on subjecting to selenium insertion reaction followed by aerial oxidation affords the related diselenide in good yield. Reaction of BF3 complexed pyridylselenolate anion (4a/4b/4c) with diiodomethane gives the corresponding bis(2-pyridylseleno)methane. The dilithiation of 4-picolinium-/pyridinium-BF3 adduct (2c/2d) followed by reaction with 2.2 equiv. of selenium and iodomethane affords the related 2,6-bis(methylselenenyl)pyridine and 2-(methylselenenyl)pyridine in varying proportions. Preparation of tris(methylselenenyl) derivatives of 1a and 1c have been given in the present study. LiAlH4 has also been utilized to synthesize unsymmetrical monoselenides from the corresponding diselenides. Single crystal X-ray studies of bis(4,5-dimethyl-2-pyridyl) diselenide (5a), 3,4-dimethyl-2,6-bis(methylselenenyl)pyridine (9a), 4-methyl-2,6-bis(methylselenenyl)pyridine (9c), 2,6-bis(methylselenenyl)pyridine (9d) and 4-methyl-2,6-bis(methylselenenyl)-4-(methylselenenylmethyl)pyridine (12a) have also been carried out. The crystal data of these compounds reveals that the instances of Se center dot center dot center dot Se secondary interactions decreases with the increase in the number of methyl group attached to the pyridine ring. (C) 2012 Elsevier B. V. All rights reserved.
keywords
ORGANOSELENIUM COMPOUNDS; CRYSTAL-STRUCTURES; DISELENIDE; DERIVATIVES; CHEMISTRY
subject category
Chemistry
authors
Dhau, JS; Singh, A; Singh, A; Sooch, BS; Brandao, P; Felix, V
our authors
Paula Cristina Ferreira da Silva Brandão
Assistant Researcher
Vítor Félix
Associate Professor with Aggregationacknowledgements
We are thankful to the CSIR, New Delhi, India, for financial support. Additional support from SAP by UGC, New Delhi, is also acknowledged. We are also thankful to Mr. Avtar Singh, CIL, Punjab University, Chandigarh, for NMR spectra.