A mild conversion of phenylpropropnoid into rare phenylbutanoids: (E)-4-(2,4,5-trimethoxyphenyl)but-1,3-diene and (E)-4-(2,4,5-trimethozypheny)but-1-ene occuring in Zingiber cassumunar

(E)-4-(2',4',5'-trimethoxyphenyl)but-1,3-diene (4) and (E)-4-(2',4',5'-trimethoxyphenyl)but-1-ene (6), bioactive phenylbutanoids of Zingiber cassumunar, were synthesized exclusively with trans geometry. Treatment of methylmagnesium iodide with (E)-2',4',5'-trimethoxycinnamaldehyde (2), an oxidized product of abundantly available toxic (Z)-phenylpropanoid (1) of Acorus calamus, gave (E)-4-(2',4',5'-trimethoxyphenyl)but-3-en-2-ol (3) which upon dehydration with copper sulphate/silica gel under microwave irradiation for 3 min afforded 4 in 58% yield. Further, catalytic hydrogenation of 4 with 10% Pd/C afforded 4-(2',4',5'-trimethoxyphenyl)butane (5) which upon dehydrogenation with DDQ/SiO2 afforded hypolipidemic 6 in 54% yield.     

Unusually efficient quenching of the fluoroscence of an energy transfer-based optical sensor for oxygen

A two-fluorophore system consisting of pyrene as donor and perylene as energy acceptor undergoes efficient energy transfer when pyrene is electronically excited. The excitation wavelength was that of pyrene and fluorescence was monitored at the emission wavelength of perylene. The fluorescence of pyrene is strongly quenched by oxygen, but that of perylene is not. The two-fluorophore system, in contrast, is very strongly quenched, with a 4-fold increase in the Stern-Volmer quenching constant as compared to the quenching of pyrene, as a result of the effect of oxygen on the formation of the donor-acceptor exciplex, and quenching by oxygen. The results are used to design a fluorescence-based optical oxygen sensor which offers a sensitivity greatly exceeding that of existing oxygen probes.     

Some Novel Dinuclear phenylboronates of biologically potent β‐enaminoesters: Synthesis,Spectroscopic characterization,antimicrobial activity and their antiandrogenic effect

Organoboron derivatives of biologically potent β‐enamino esters of the type [Where R = CH₃(1a), C₂H₅ (1b), C₃H₇(1c) and C (CH₃)₃ (1d)] have been prepared by the reactions of β‐enamino esters and Phenyl boronic acid [PhB (OH)₂] in 1:2 molar ratio in refluxing tetrahydrofuran (THF). All these derivatives have been characterized by physico‐chemical properties, elemental analyses and molecular weight measurements. The structures of these compounds have been proposed on the basis of IR, ¹H, ¹³C, ¹¹B NMR spectral data and GC‐mass spectrometry. Phenyl boronic acid, β‐enamino esters and their respective phenylboronates derivatives have been screened for the antibmicrobial activities against pathogenic bacteria (B. subtilis and E. coli) and fungi (A. niger and P. peniculosum) to access their growth inhibiting potential. In addition to this, antiandrogenic effect of Ligand, L^aH₂ and its boron derivative (1a) has also been tested in male albino rats.     

Spectroscopy at very high pressures: Part 27. Raman study of the second-order phase transitions in sodium nitrite and sodium nitrate

Raman spectra of NaNO₂ have been studied as a function of hydrostatic pressure to 40 kbar at 295 and 348 K. Slight changes in slope of mode frequency versus pressure plots support the view that a structural anomaly exists at 9 ± 1 kbar. The absence of qualitative changes in the Raman spectra allow the space group of NaNO₂ IV to be specified as one of P1, P2, B2, Pm or Bm. The Raman spectrum of NaNO₃ has been studied to 87 kbar. The changes observed are fully consistent with a second-order transition to a phase with symmetry C⁶_3v, as indicated by previous X-ray work, although the transition is sluggish.     

Kinetics and mechanism of the oxidation of some α‐hydroxy acids by 2,2′‐bipyridinium chlorochromate

The oxidation of glycolic, lactic, malic, and a few substituted mandelic acids by 2,2′‐bipyridinium chlorochromate (BPCC) in dimethylsulphoxide leads to the formation of corresponding oxoacids. The reaction is first order each in BPCC and the hydroxy acids. The reaction is catalyzed by the hydrogen ions. The hydrogen ion dependence has the form: k_obs = a + b [H⁺]. The oxidation of α‐deuteriomandelic acid exhibited a substantial primary kinetic isotope effect (k_H/k_d = 5.29 at 303 K). Oxidation of p‐methylmandelic acid was studied in 19 different organic solvents. The solvent effect has been analyzed by using Kamlet's and Swain's multiparametric equations. A mechanism involving a hydride ion transfer via a chromate ester is proposed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 248–254, 2002     

Microwave spectrum,centrifugal distortion constants,dipole moment and quadrupole coupling constants of pentafluoropyridine

Pentafluoropyridine has been analysed in the frequency range of 8 to 18 GHz at dry ice temperature, using a conventional 100 kHz Stark modulated microwave spectrometer. The rotational constants and centrifugal distortion constants are A = 1481.539 ± 0.003 MHz, B = 1075.348 ± 0.004 MHz and C = 623.101 ± 0.001 MHz; and d_J = ?0.39 ± 0.06 kHz, d_JK = 1.86 ± 0.27 kHz, d_K = 0.70 ± 0.1 kHz, d_EJ = (0.3 ± 0.03) × 10^?6 and d_EK = (?1.5 ± 0.2) × 10^?6. The electric dipole moment has been found to be 0.98 ± 0.08 D and the values of the quadrupole coupling constants are x_aa = 1.94 ± 0.22 MHz, x_bb = ?4.08 ± 0.06 MHz and x_cc = 2.14 ± 0.22 MHz. A simple analysis based on Townes and Dailey theory points to a considerable increase in the π-electron density and excess charge on the nitrogen site.     

Theoretical study of structure,vibrational and electronic spectra of isomers of methyl-3-methoxy-2-propenoate

A systematic quantum mechanical study of the possible conformations, their relative stabilities, vibrational and electronic spectra and thermodynamic parameters of methyl-3-methoxy-2-propenoate has been reported for the electronic ground (S₀) and first excited (S₁) states using time-dependent and time-independent Density Functional Theory (DFT) and RHF methods in extended basis sets. Detailed studies have been restricted to the E-isomer, which is found to be substantially more stable than the Z-isomer. Four possible conformers c′Cc, c′Tc, t′Cc, t′Tc, of which the first two are most stable, have been identified in the S₀ and S₁ states. Electronic excitation to S₁ state is accompanied with a reversal in the relative stability of the c′Cc and c′Tc conformers and a substantial reduction in the rotational barrier between them, as compared with the S₀ state. Optimized geometries of these conformers in the S₀ and S₁ states are being reported. Based on suitably scaled RHF/6-31G^** and DFT/6-311G^** calculations, assignments have been provided to the fundamental vibrational bands of both these conformers in terms of frequency, form and intensity of vibrations and potential energy distribution across the symmetry coordinates in the S₀ state. A complete interpretation of the electronic spectra of the conformers has been provided.