Control of Regiochemistry in Photodimerization through Micellar Preorientational Effect: 2-Substituted Naphthalenes

Photodimerization of 2-substituted naphthalenes in organic solvents has been well explored. In contrast to their behavior in organic solvents, in anionic and cationic micellar media enhanced reactivity and pronounced regioselectivity are observed. Reactivity enhancement in micellar media is attributed to the local concentration effect. Enhanced reactivity in CTAC and DTAC compared to CTAB micelles is attributed to the counterion effect, and the regioselective photodimerization observed in anionic and cationic micelles leading exclusively to the cis dimer or the products derived therefrom is rationalized on the basis of the preorientational effect of micelles.

Rearrangements in the cerium(IV) and manganese(III) oxidations of substituted naphthalenes and the nih shift mechanism

Ceric ammonium sulphate oxidation of 1- and 1,4- disubstituted naphthalenes gives 2- and/or 2,3- disubstituted 1,4- naphthoquinones through migration of substituents (D, Br, Ph). Similar rearrangements are also observed in the manganese(III) oxidation and also in the anodic oxidation of these substrates. The results are consistent with the proposal that these oxidations go through the formation of radical cation followed by reaction with H2O and further oxidation of the radical to the carbocationic intermediate on the way to the corresponding 1,4-naphthoquinone. Oxidation of 1,4-diphenylnaphthalene gives 2,3-diphenyl-1,4-naphthoquinone or 4-hydroxy- 2,4- diphenyl - 1(4)R - naphthalenone. The results are in accordance with the conclusion that such rearrangements do not require prior formation of arene oxide intermediates, originally proposed for the NM shift mechanism.

Oxidation of substituted benzylic hydrocarbons and naphthalenes by peroxydisulphate in the presence of metal ions

Oxidations of various substituted benzylic hydrocarbons with peroxydisulphate in the presence of metal ion catalysts like iron, nickel, copper, cobalt, silver and cerium were examined. Among the metal ions copper (II) catalysed reaction gives products in excellent yield, whereas oxidation of naphthalene and substituted naphthalenes gives low to moderate yield of the products with peroxydisulphate- copper (II).

Naphthalenes Image microwave irradiation induced rearrangement on montmorillonite K-10

Irradiation of 4-aryl-4-alkylhex-5-en-2-ones (e.g. 1a) or 5-aryl-4-alkylhex-5-en-2-ones (e.g. 2a) adsorbed on montmorillonite K-10 in a commercial microwave oven furnishes the multialkylated naphthalenes (e.g. 3).

Isomeric identification of methylated naphthalenes using gas phase infrared spectroscopy

We report gas phase mid-infrared spectra of 1- and 2- methyl naphthalenes at 0.2 cm(-1) resolution. Assignment of observed bands have been made using scaled quantum mechanical (SQM) calculations where the force fields rather the frequencies are scaled to find a close fit between observed and calculated bands. The structure of the molecules has been optimized using B3LYP level of theory in conjunction with standard 6-311G** basis set to obtain the harmonic frequencies. Using the force constants in Cartesian coordinates from the Gaussian output, scaled force field calculations are carried out using a modified version of the UMAT program in the QCPE package. Potential energy distributions of the normal modes obtained from such calculations helped us assign the observed bands and identify the unique features of the spectra of 1- and 2-MNs which are important for their isomeric identification.

Regioselective Deiodination of Thyroxine by Iodothyronine Deiodinase Mimics: An Unusual Mechanistic Pathway Involving Cooperative Chalcogen and Halogen Bonding

Iodothyronine deiodinases (IDs) are mammalian selenoenzymes that catalyze the conversion of thyroxine (T4) to 3,5,3'-triiodothyronine (T3) and 3,3',5'-triiodothyronine (rT3) by the outer- and inner-ring deiodination pathways, respectively. These enzymes also catalyze further deiodination of T3 and rT3 to produce a variety of di- and monoiodo derivatives. In this paper, the deiodinase activity of a series of pen-substituted naphthalenes having different amino groups is described. These compounds remove iodine selectively from the inner-ring of T4 and T3 to produce rT3 and 3,3'-diiodothyronine (3,3'-T2), respectively. The naphthyl-based compounds having two selenols in the pen-positions exhibit much higher deiodinase activity than those having two thiols or a thiol selenol pair. Mechanistic investigations reveal that the formation of a halogen bond between the iodine and chalcogen (S or Se) and the pen-interaction between two chalcogen atoms (chalcogen bond) are important for the deiodination reactions. Although the formation of a halogen bond leads to elongation of the C-I bond, the chalcogen bond facilitates the transfer of more electron density to the C-I sigma* orbitals, leading to a complete cleavage of the C-I bond. The higher activity of amino-substituted selenium compounds can be ascribed to the deprotonation of thiol/selenol moiety by the amino group, which not only increases the strength of halogen bond but also facilitates the chalcogen chalcogen interactions.