Kinetics of ceric ion oxidation of naphthalene and its derivatives. Formation of the radical cation intermediate in the rate limiting step

Ceric ammonium sulfate, CAS, oxidizes naphthalene to 1,4-naphthoquinone in essentially quantitative yield in CH3CN-dil. H2SO4. Stoichiometric studies indicate that 6 mol of CAS are required for the oxidation of 1 mol of naphthalene to 1,4-naphthoquinone. Kinetic investigations reveal that the reaction takes place through initial formation of a 1:1 complex of naphthalene and cerium(IV) in an equilibrium step followed by slow decomposition of the complex to naphthalene radical cation. Kinetic results on the effects of acid strength, polarity of the medium, temperature and substituents are in accordance with this mechanism. Further conversion of the radical cation into 1,4-naphthoquinone takes place in fast steps involving a further 5 mol of cerium(IV) and 2 mol of H2O.

Recognition of Polycyclic Aromatic Hydrocarbons and Their Derivatives by the 1,3-Dinaphthalimide Conjugate of Calix4]arene: Emission, Absorption, Crystal Structures, and Computational Studies

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants as well as well-known carcinogens. Therefore, it is important to develop an effective receptor for the detection and quantification of such molecules in solution. In view of this, a 1,3-dinaphthalimide derivative of calix4]arene (L) has been synthesized and characterized, and the structure has been established by single crystal XRD. In the crystal lattice, intermolecular arm-to-arm pi center dot center dot center dot pi overlap dominates and thus L becomes a promising receptor for providing interactions with the aromatic species in solution, which can be monitored by following the changes that occur in its fluorescence and absorption spectra. On the basis of the solution studies carried out with about 17 derivatives of the aromatic guest molecular systems, it may be concluded that the changes that occur in the fluorescence intensity seem to be proportional to the number of aromatic rings present and thus proportional to the extent of pi center dot center dot center dot pi interaction present between the naphthalimide moieties and the aromatic portion of the guest molecule. Though the nonaromatic portion of the guest species affects the fluorescence quenching, the trend is still based on the number of rings present in these. Four guest aldehydes are bound to L with K-ass of 2000-6000 M-1 and their minimum detection limit is in the range of 8-35 mu M. The crystal structure of a naphthaldehyde complex, L.2b, exhibits intermolecular arm-to-arm as well as arm-to-naphthaldehyde pi center dot center dot center dot pi interactions. Molecular dynamics studies of L carried out in the presence of aromatic aldehydes under vacuum as well as in acetonitrile resulted in exhibiting interactions observed in the solid state and hence the changes observed in the fluorescence and absorption spectra are attributable for such interactions. Complex formation has also been delineated through ESI MS studies. Thus L is a promising receptor that can recognize PAHs by providing spectral changes proportional to the aromatic conjugation of the guest and the extent of aromatic pi center dot center dot center dot pi interactions present between L and the guest.

Bridgehead substitution of 1-methoxybicyclo[2.2.2]oct 5-en-2-one derivatives: towards the synthesis of (±)-allo-cedrol [khusiol]1

Preparation of the key intermediates, 11 and 21, required for the synthesis of (+/-)-allo-cedrol (khusiol) is reported by a novel methodology involving the substitution at the bridgehead position of 1-methoxybicyclo[2.2.2]oct-5-en-2-one derivatives

Studies on pyridinium hexafluorostannate and its derivatives

Pyridinium hexafluorostannate, (C5H5NH)2SnF6, has been prepared by the reaction of stannous chloride or tin metal with pyridinium poly(hydrogen fluoride), PPHF, and identified by chemical analysis, IR and NMR (H-1, F-19, C-13). Making use of (C5H5NH)2SnF6 as a precursor, the following important hexafluorostannate salts have been synthesized in high yields at room temperature by ionic exchange: M2SnF6 (M = NH4, Na, K, Rb, Cs) and BaSnF6. These salts have been characterised by chemical analysis and infrared spectroscopy. Indexed powder X-ray diffraction data for Na2SnF6, Rb2SnF6 and Cs2SnF6 have been reported.

Asymmetric Diels-Alder Reactions of Chiral Acrylates of Cholic Acid Derivatives

New steroid-based chiral auxiliaries 6, 9, and 12 have been synthesized from readily available cholic acid. These new chiral auxiliaries place the reactive and the shielding sites in a 1,5 relationship to each other. Diels-Alder reaction of cyclopentadiene with corresponding acrylate esters (7, 10, and 13) have been examined. Acrylates 7 and 10 yielded cycloadducts with 29-88% diastereomeric excess with excellent endo selectivity in the presence of an excess of Lewis acids such as AlCl3, BF3.OEt(2), FeCl3, SnCl4, TiCl4, and ZnCl2. Treatment of acrylate 7 with cyclopentadiene in the presence of BF3.OEt(2) at -80 degrees C gave the endo adduct (>99%) with 88% de. Lewis acid catalyzed and uncatalyzed reactions of acrylates 7 and 10 with cyclopentadiene yielded cycloadducts with opposite stereochemistry. The chiral auxiliary was recovered in a nondestructive manner only via iodolactonization. Acrylate ester of alcohol 12 did not show any selectivity in either catalyzed and uncatalyzed reactions with cyclopentadiene. The presence of a flat aromatic surface at C-7 of the steroid was found to be essential to effect high diastereoselection.

Enantioselective synthesis of both (+)- and (-)-derivatives of bicyclo[4.3.0]nonan-8-one and 3,8-diones from R-carvone

Enantioselective synthesis of both the enantiomeric forms of the hydrindane derivatives mentioned in the title, potential chiral precursors in terpenoid synthesis, starling from R-carvone employing two different cyclopentannulation methodologies is described.

Nitrogen Derivatives Of C-60 And C-70 - Interaction Of Fullerenes With Nitrogen In Gas-Phase

Mass spectrometric studies show that contact-arc vaporization of graphite in a partial atmosphere of N2 or NH3 yields nitrogenous products tentatively assigned to species such as C70N2, C59N6, C59N4 and C59N2 involving addition of or substitution by nitrogen along with the species due to C2 and C4 losses. Mass spectrometry and other techniques have been employed to identify products of the nucleophilic addition of aliphatic amines to C60 and C70 in solution phase.

Physics Of Undoped And Doped C-60 Fullerene

This paper contains a review of the physical properties of the undoped and alkali-doped C60 materials, including their crystal structure, electronic, optical and vibrational properties and the effect of pressure on the crystal and electronic structure. The mechanisms of superconductivity in alkali-doped C60 in terms of phonon mediated electron pairing vis-a-vis electronic interaction effects are discussed.

Solubilities of Benzene Derivatives in Supercritical Carbon Dioxide

The solubilities of benzene derivatives in supercritical carbon dioxide was determined by the saturation method over the pressure range (9.5 to 14.5) MPa. The solubilities were determined at (308 and 313) K for 1-chloro-2,4-dinitrobenzene and (308, 318, and 328) K for m-dinitrobenzene. At 308K, the solubility (in mole fraction) of 1-chloro-2,4-dinitrobenzene varied from (2.83 to 5.88).10(-3) while the solubility of m-dinitrobenzene increased from (2.05 to 5.54).10(-3) as the pressure increased from (9.5 to 14.5) MPa. However, the solubilities of both compounds decreased with increasing temperature. Models based on the solubility parameter and semiempirical models such as the Mendez-Santiago-Teja model, the Gordillo model, and the association model, were used to correlate the experimental solubility data for the benzene derivatives.

Non-linear optical response of rutile-related oxides, LiM(V)M(VI)O(6), and their derivatives obtained by ion-exchange and intercalation

Polycrystalline samples of oxides of the general formula LiM(V)M(VI)O(6) (M(V) = Nb, Ta; M(VI) = Mo, W), crystallizing in a non-centrosymmetric (space group P (4) over bar 2(1)m) trirutile structure, exhibit second harmonic generation (SHG) of 1064 nm radiation with efficiencies 15-45 times that of alpha-quartz; interestingly, the SHG response is retained by the protonated derivatives HM(V)M(VI)O(6) . xH(2)O, and their n-alkylamine intercalates as well.

Phosphate derivatives of 123 cuprates of the formula LnSr(2)Cu(3)O(7) (Ln=Gd, Dy, Ho)

Partial substitution of Cu in the chain by the phosphate ion stabilizes LnSr(2)Cu(3)O(7) (Ln = Gd, Dy or Ho) in the 123 structure. The LnSr(2)Cu(2.8)(PO4)(0.2)O-y derivatives exhibit incommensurately modulated structures. The holmium oxy-phosphate derivative has been rendered superconducting by the partial substitution of Ho by Ca.

Reduction of quinolines to 1,2,3,4-tetrahydro derivatives employing a combination of NaCNBH3 and BF3.OEt(2)

A regiospecific reduction of quinolines (and 1,10-phenanthroline) into the corresponding 1,2,3,4-tetrahydro derivatives using a combination of sodium cyanoborohydride and boron trifluoride etherate in refluxing methanol is described. Under the same conditions indole and acridine reduced to the corresponding dihydroderivatives, whereas acyl group transfer from oxygen to nitrogen atom is also noticed in the case of 8-acyloxyquinolines.

Thermal expansion studies of substituted CTP derivatives

Several new Na, Y and Zr substituted derivatives of Ca-0.5 Ti-2(PO4)(3) (CTP) have been synthesized. These derivatives retain the hexagonal structure of the parent (CTP) compound with minor changes in lattice parameters. Linear thermal expansion coefficients (alpha) have been obtained using a high sensitivity dilatometer.

DNA binding properties of some cationic acridine derivatives

Four cationic acridine derivatives have been synthesized. The positively charged amine residue in one of these is connected directly on to the acridine nucleus and in three other acridines, the amines are connected via a 9-CH2 unit to acridine. We have investigated the binding of these acridines with mammalian DNA by absorption titration, UV- and induced-CD spectroscopy and competitive ethidium bromide displacement fluorescence assay. The effects on the DNA duplex denaturation melting temperatures upon binding of each one of these are also examined. The results obtained herein clearly show that the introduction of a -CH2 group in the im mediate vicinity of the interrelation moiety introduces alterations in the DNA binding characteristics of the resulting acridines.

Pyridinidm Hexafluorotitanate and its Derivatives

Pyridinium hexafluorotitanate, (C5H5NH)(2)TiF6, has been prepared by the reaction of titanium metal with pyridinium poly(hydrogen fluoride), PPHF, at room temperature. Making use of (C5H5NH)(2)TiF6 as a precursor, ammonium and alkali metal hexafluorotitanates, M(2)TiF(6) (M = NH4, Na, K, Rb and Cs) have been synthesized by metathesis. These hexafluorotitanates have been characterized by chemical analyses, infrared and NMR (H-1 and F-19) spectroscopy and powder X-ray diffraction methods. Indexed powder X-ray diffraction data for Rb2TiF6 and Cs2TiF6 have been reported.