ZnBr2 catalyzed domino Knoevenagel-hetero-Diels–Alder reaction: An efficient route to polycyclic thiopyranoindol annulated [3,4-c]quinolone derivatives

Various novel polycyclic thiopyranoindol annulated [3,4-c]quinolone derivatives were synthesized via domino Knoevenagel-hetero-Diels–Alder reactions of indoline-2-thions and novel N-acrylated anthranilaldehydes in refluxing ethanol as a solvent in the presence of 20 mol% ZnBr₂ as a Lewis acid catalyst. All reactions proceed with high yields with excellent regio- and stereoselectivity.     

Iron-catalyzed selective reduction of nitro compounds to amines

An efficient reduction of the nitro group with a catalytic amount of Fe(acac)₃ and TMDS in THF at 60 °C affording the corresponding amine is described.     

Sequences of orthogonal Laurent polynomials,bi-orthogonality and quadrature formulas on the unit circle

In this paper, the construction of orthogonal bases in the space of Laurent polynomials on the unit circle is considered. As an application, a connection with the so-called bi-orthogonal systems of trigonometric polynomials is established and quadrature formulas on the unit circle based on Laurent polynomials are studied.     

Ruthenium complexes of aminophosphine ligands and their use as pre-catalysts in the transfer hydrogenation of aromatic ketones: X-ray crystal structure of thiophene-2-(N-diphenylthiophosphino)methylamine

Reaction of thiophene-2-methylamine with one or two equivalents of PPh₂Cl in the presence of NEt₃, proceeds in thf to give thiophene-2-(N-diphenylphosphino)methylamine, 1a and thiophene-2-(N,N-bis(diphenylphosphino))methylamine, 2a respectively, under anaerobic conditions. Oxidations of 1a and 2a with aqueous hydrogen peroxide, elemental sulfur or gray selenium in thf gives the corresponding oxides, sulfides and selenides [Ph₂P(E)NHCH₂-C₄H₃S] (E: O 1b, S 1c, Se 1d) and [(Ph₂P(E))₂NCH₂-C₄H₃S], (E: O 2b, S 2c, Se 2d) respectively, in high yield. Furthermore, two novel Ru(II) complexes with the P-N ligands 1a and 2a were synthesized starting with the complex [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂. The complexes were fully characterized by analytical and spectroscopic methods. ³¹P-{¹H} NMR, DEPT, ¹H-¹³C HETCOR or ¹H-¹H COSY correlation experiments were used to confirm the spectral assignments. The molecular structure of thiophene-2-(N-diphenylthiophosphino)methylamine was also elucidated by single-crystal X-ray crystallography. Following activation by NaOH, compounds 3 and 4 catalyze the transfer hydrogenation of acetophenone derivatives to 1-phenylethanol derivatives in the presence of iso-PrOH as the hydrogen source. [Ru(Ph₂PNHCH₂-C₄H₃S)(η⁶-p-cymene)Cl₂], 3 and [Ru((PPh₂)₂NCH₂-C₄H₃S)(η⁶-p-cymene)Cl]Cl, 4 complexes are suitable catalyst precursors for the transfer hydrogenation of acetophenone derivatives in 0.1 M iso-PrOH solution. Notably 4 acts as an excellent catalyst giving the corresponding alcohols in excellent conversions up to 99% (TOF ? 744 h⁻¹). This transfer hydrogenation is characterized by low reversibility under the experimental conditions.     

Odd-even effects on the structure, stability, and phase transition of alkanethiol self-assembled monolayers

Molecular dynamics simulations were conducted to predict the structural properties and phase transition temperatures of n-alkanethiols CH(3)(CH(2))(n-1)SH (Cn, 4 ≤ n ≤ 22) self-assembled monolayers (SAMs) on Au (111) surfaces. We studied the effects of chain length on the structural properties, including tilt and orientation angles, and on phase transition temperature. We found clear dependence of the structural properties, on both the number of carbon atoms, n; and on n being odd or even. Alkanethiols with n ≤ 7 show liquid-like behavior and large rotational mobility, whereas those with n ≥ 12 are well-ordered and stable. For 12 ≤ n ≤ 15, odd-even effects are observed, where for n = odd, larger tilt angles, oriented in the direction of their next next nearest neighbor (NNNN), and for n = even, lower tilt angles, mostly tilted toward next nearest neighbor (NNN), were observed. For 15 ≤ n ≤ 19, we find tilt angle and orientation to be independent of n. For all alkanethiols, a gradual decrease of the tilt angle occurred by increasing the temperature from 300 to 420 K. Order-disorder phase transitions occurred at a certain temperature. This was signified by abrupt instabilities in the tilt orientation angle. This transition temperature showed an enhancement of ～67-100 °C over the melting point of the corresponding n-alkane bulk system. This enhancement depended on n, and was larger for n = odd. Overall, we found that odd alkanethiols show better structural and thermal stability, and smaller gauche defects.     

Relativistic energies and transition probabilities for some highly excited levels in singly ionized indium

For some excited levels (n?8), the energies, wavelengths, oscillator strengths and transition probabilities calculations in singly ionized indium have been calculated within the framework of multiconfiguration Hartree-Fock approximation with relativistic corrections (Breit-Pauli Hamiltonian). The wavefunctions and some relativistic corrections have been obtained using MCHF-BP atomic package. Comparisons with other calculations and experiments are presented.     

Generating sets of finite singular transformation semigroups

J.M. Howie proved that $\operatorname {Sing}_{n}$ , the semigroup of all singular mappings of {1,…,n} into itself, is generated by its idempotents of defect 1 (in J. London Math. Soc. 41, 707–716, 1966). He also proved that if n≥3 then a minimal generating set for $\operatorname {Sing}_{n}$ contains n(n?1)/2 transformations of defect 1 (in Gomes and Howie, Math. Proc. Camb. Philos. Soc. 101. 395–403, 1987). In this paper we find necessary and sufficient conditions for any set for transformations of defect 1 in $\operatorname {Sing}_{n}$ to be a (minimal) generating set for $\operatorname {Sing}_{n}$ .