Meroterpenoids—III : Psoralea corylifolia linn.—3. Synthesis of (±)-bakuchiol methyl ether

A synthesis of (±)-bakuchiol methyl ether, involving Claisen rearrangement of geranyl vinyl ether as the key step, is described. Further thermal reorganisation of the intermediate 3-vinyl-citronellal is discussed.     

Polymethine dyes — Indolo[3,2-d]thiazole derivatives

New polymethine dyes with an indolo[3,2-d]thiazole residue are described, and their spectral properties are discussed. Replacement of the vinylene group in the naphtho[1,2-d]thiazole residue by an NH group leads to a considerably greater bathochromic shift of the absorption maximum of carbo- and merocyanines as compared with replacement by a sulfur atom. The basicity of the indolo[3,2-d]thiazole residue is higher than the basicity of the naphtho[1,2-d]-thiazole and thionaphtheno[3,2-d]thiazole residues.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1606–1610, December, 1972.     

Methyl-substituted heterocyclic bases containing condensed selenonaphthene rings

The synthesis of 2-methylselenonaphtheno[2,3-d]thiazole and 2-methylselenonaphtheno[2,3-d]-oxazole is described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 37–38, January, 1971.     

Use of long-chain alkylamines for preconcentration and determination of traces of molybdenum, tungsten and rhenium by atomic-absorption spectroscopy-II: molybdenum in soils, sediments and natural waters

Molybdenum is extracted as the thiocyanate complex with the quaternary long-chain aliphatic amine Aliquat 336 in chloroform, followed by evaporation of the solvent, dissolution in MIBK, and atomic-absorption spectroscopy. The method is simple, rapid and sensitive, with few interference problems for the determination of the Mo content of soils and sediments in the range 0.1-1.0 ppm with a relative standard deviation better than 5% when 1-g samples are used. Quantitative extraction from large volumes of aqueous solution has also been confirmed, allowing the determination of Mo in natural waters in the ppM range.     

Calculation of the 1J(PP) angular dependence in P2H4

Using the results obtained from an MO SCF ab initio calculation on P₂H₄ in four different conformations, the ¹J(PP) NMR coupling constants have been calculated. The ¹J(PP) values are highly dependent upon the rotational angle φ (?238.0 Hz in the eclipsed conformation, 10.9 Hz in the staggered one). The shape of the theoretical ¹J(PP) plot seems to be in good agreement with experimentally measured ¹J(PP) values.     

Studies of solvent effects

The effect of water on the conformational preferences of acetylcholine has been studied within the discrete, the continuum and the combined discrete-continuum models described in parts I and II of this series. All the models lead to the conclusion that the trans-gauche form which is, following refined quantum-mechanical computations, the intrinsically preferred one and the one observed in the crystal of acetylcholine and of a number of analogues should remain also the preferred conformation in water. This result agrees with NMR studies. The results of the empirical discrete model used here compare favorably to those obtained by an ab initio super-molecule treatment. The continuum model utilized here represents a net improvement above such models utilized in other works.     

Relativistic molecular orbitals for the double group D3h

Relativistic symmetry orbitals are given for the double group D_3h. For atomic orbitals at the symmetry center a general expression is presented. The atomic orbitals of the s, p_½, and p_3/2 variety outside the center are also considered. The representation matrices are given in explicit form.     

The determination of sulphur in copper,nickel and aluminium alloys by proton activation analysis

The ³⁴S(p, n)^34mCl reaction induced by 13-MeV protons is used for the determination of sulphur in copper, nickel and aluminium alloys. The ^34mCl is separated by repeated precipitation as silver chloride. The results obtained were 3.08 ± 0.47, 1.47 ± 0.17 and <1μg g^-1 for copper, nickel and aluminium alloys, respectively.     

Crystal and molecular structure of 5-ethyl-5,10-dihydrido-10,10-diphenylphenazasiline

The structure of 5-ethyl-5,10-dihydro-10,10-diphenylphenazasiline has been determined from three-dimensional X-ray data collected by counter methods. The compound in the monoclinic space group P2₁/b with a 10.782(5), b 22.642(9), c 8.830(4) Å and γ 74°41′(2). The observed and calculated densities (Z = 4) are 1.22 and 1.21 g cm^-3, respectively. Anisotropic(Si, N, C)-isotropic block-diagonal least squares refinement gave a conventional R factor of 3.9% for 1871 reflections with I>2σ(I). The central six-membered ring of the tricyclic system adopts a boat conformation; the dihedral angle between the benzo-group planes is 157.3°. The CSiC angle in the heterocycle is 101.1(1)°; the mean SiC bond length is 1.850(2) Å (in the cycle) and 1.862(2) Å (with Ph group). The nitrogen atom is displaced 0.05 Å from the plane of the adjacent carbon atoms; the sum of the angle about N is 359.7°.     

A comparison of SCF-Xα and extended Hückel methods for metal clusters

A comparison of some results from Xα-scattered wave (Xα-SW) and extended Hückel (EH) calculations for metal clusters is given. It is found that small clusters of atoms (≈ 13 atoms) using the Xα-SW method reproduce many of the features of the electronic structure of the bulk metals, whereas this is not the case for the same clusters using the EH method. A more systematic approach to EH parametrizations is suggested in order to make this method a more viable approach to treating metal clusters.