Synthesis and complexation studies of intra annularly linked bicyclic cyclophanes

The cyclophanes derived from 2,6-bis(chloromethyl)benzoquinone and suitable dithiols were reduced with sodium dithionate and then further coupled with various dibromides to give intra annularly linked bicyclic cyclophanes, which forms charge transfer complexes with TCNQ and TCNE.     

Synthesis and photoluminescence properties of some novel fluorenophanes

Fluorenophanes derived from 2,7-bis-(bromomethyl)-9,9′-diheptyl-9H-fluorene and various diols exhibit excellent photoluminescence properties.     

One-Pot Synthesis of Heterocyclic beta-Chlorovinyl Aldehydes Using Vilsmeier Reagent

3-Chloro-1H-indole-2-carboxaldehydes are obtained in moderate yields by the one-pot reaction of various substituted 2-[(carboxymethyl)amino]benzoic acids (1a-d) using Vilsmeier reagent (DMF/POCl(3)). The benzfused acyclic diacids analogous to 1a in which nitrogen was replaced by oxygen and sulfur also underwent the reaction smoothly. 3-Chloro-1H-pyrrole-2,4-dicarboxaldehyde was obtained as the only product by the reaction of N-carboxymethyl beta-alanine.     

Synthesis, structure, and theoretical study of the nonclassical [CuTe(7)](3-) anion

The compound [PPh(4)](2)[NEt(4)][CuTe(7)] has been synthesized from the reaction of CuCl with a polytelluride solution in dimethylformamide at room temperature. The compound crystallizes with two formula units in the triclinic space group P(-)1 in a cell with dimensions a = 8.9507(18) A, b = 14.714(3) A, and c = 23.277(5) A and alpha= 86.32(3) degrees, beta= 80.17(3) degrees, and gamma= 75.63(3) degrees (T = -120 degrees C). Ab initio calculations indicate that the nonclassical [CuTe(7)](3)(-) anion is the result of joining Te(3)(2-) and [CuTe(4)](1-) fragments through donor-acceptor interactions.     

The use of McMurry coupling for the synthesis of indolophanes and cis-stilbenophanes

Treatment of 2 equiv of indole-3-aldehyde with o, m, p-xylyl, 2,5-dimethoxy-p-xylyl dibromides and 4,4′-bis(bromomethyl)-1,1′-biphenyl gave the bisalkylated products, which underwent McMurry coupling with low valent titanium to give indolophanes. Various cis-stilbenophanes with m-terphenyl building blocks were also synthesized by application of the McMurry coupling technique.     

Triphase catalysis. I. Kinetics and mechanism of alkylation of phenylacetonitrile with alkyl halides catalyzed by aqueous naoh and polymer-supported benzyltriethylammonium chloride

The alkylation and cycloalkylation of phenylacetonitrile (PAN) with excess of 1-bromobutane and 1,4-dibromobutane respectively catalyzed by aqueous NaOH and insoluble polystyrene-bound benzyltriethylammonium chloride were studied and the rates depend upon several experimental parameters. The rate of cycloalkylation of PAN is five times faster than the alkylation and the former proceeds even in the absence of the solid catalyst. Both alkylation and cycloalkylation gave higher rates in reverse addition method than in direct addition. Deprotonation of PAN by hydroxide ion takes place without participation of the polymeric catalyst. The electrostatic force between the positive charge on the nitrogen atom of catalyst and carbanion is responsible for alkylation of active nitrile with polystyrene-bound phase-transfer catalyst. The rates of both the reactions increase with increased stirring speed, ring substitution, hydroxide ion concentration and catalyst amount and decrease with increased particle size and the degree of cross-linking of the polymer. Apparent activation energies for the reactions were calculated. The kinetic results are discussed in terms of mass transfer and a combination of intraparticle diffusion and intrinsic reactivity limitations of the rates.     

A Novel Synthesis of tert- Alkyl Sulfides

tert- Alkyl sulfides are conveniently prepared from α-(1H-benzotriazol-1-yl)alkyl sulfides by displacement of the 1H-benzotriazol-1-yl group with Grignard reagents. The 1-[α-(alkylthio)alkyl]- and 1-[α-(arylthio)alkyl]-1H-benzotriazole intermediates are easily available by several routes: (i) displacement of the halogen from appropriate halides by sodium salts of thiols, (ii) condensation of 1H-benzotriazole and thiols with carbonyl compounds, or (iii) lithiation of N-substituted 1H-benzotriazoles and subsequent treatment with electrophiles.