A One-Pot Selective Synthesis of N-Boc Protected Secondary Amines: Tandem Direct Reductive Amination/N-Boc Protection

A one-pot tandem direct reductive amination of aldehydes with primary amines resulting in N-Boc secondary amines using a (Boc)(2)O/sodium triacetoxyborohydride (STAB) system is reported. The tandem procedure is efficient, selective, and versatile, giving excellent yields of N-Boc protected secondary amines even in those cases where the products are prone to intramolecular lactamization.     

Flow between torsionally oscillating disks rotating about different axes at different speeds

The flow of an incompressible viscous fluid confined between two parallel infinite disks performing torsional oscillations with the same frequency, but rotating about different axes with different speeds has been studied. The solutions are presented for the symmetric and asymmetric first harmonic and steady streaming. The interesting features of the symmetric and asymmetric flow are discussed for the cases of small and large Womersley parameter at different ratios of the rotation speeds. The forces acting on one of the disks are also calculated.

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Zusammenfassung In der vorliegenden Arbeit wird die Strömung einer zwischen zwei parallelen, unendlichen Scheiben begrenzten, inkompressiblen, viskosen Flüssigkeit untersucht; die zwei Scheiben führen Torsionsschwingungen gleicher Frequenz aus, drehen sich aber um verschiedene Achsen mit verschiedenen Geschwindigkeiten. Lösungen werden gegeben für die symmetrische und asymmetrische, erste harmonische Oberschwingung und die stationäre Strömung. Die interessanten Eigenschaften der symmetrischen und asymmetrischen Strömung werden diskutiert für die Fälle von kleinem und großem Womersley-Parameter bei verschiedenen Verhältnissen der Drehgeschwindigkeiten. Außerdem werden die Kräfte berechnet, die auf eine der Scheiben einwirken.

     

Concentration dependence of the viscoelastic properties of polystyrene-tricresyl phosphate solutions

Based on creep and creep-recovery measurements, the viscoelastic functions [J(t), J_r(t), J′(ω), J″(ω), G′(ω), G″(ω), and L(lnτ)] are presented for solutions of a narrow molecular-weight-distribution polystyrene in tri-m-tolyl phosphate in the concentration range of 1% to 100% polymer. For concentrations of 25% polymer and above, two maxima are exhibited by the retardation spectrum, L(lnτ). In the neighborhood of each of the maxima the retardation spectra of the more concentrated solutions can be superimposed by translations along both the logL and logτ axes. Reflecting the increasing width of the rubbery plateau with increasing polymer concentration, the dependence of the concentration time-scale shift factors is greater for the terminal region of response. The response of the solvent is seen at the lower concentrations and it is a less sensitive function of the concentration than that of the polystyrene. This behavior is associated with the previously reported observation of two glass-transition temperatures in the middle concentration range. For the higher concentrations, both the steady-state and rubbery-plateau compliances are inversely proportional to the square of the concentration.     

Solid-state polymerization studies of conjugated diacetylenes deca-2,8-diene-4,6-diyne-1,10-diol and derivatives

The title diacetylenic compound (D3) and its derivatives dibenzoate (D3B), dinitrobenzoate (D3mNB), ditosylate (D3PTS), and diurethane (D3PU) were synthesized and their solid-state reactivity examined under irradiation and thermal stimulation. D3, D3B, and D3PTS crystallized in reactive phases. The thermal and irradiation polymerization behavior of D3 and D3B was examined further by time-conversion curves.     

A carbohydrate-based approach for the total synthesis of strictifolione

A chiral pool approach starting with d-glucose, using the Yamaguchi protocol and a Z-selective HWE reaction followed by lactonization, has been applied to execute the total synthesis of strictifolione.     

New evidence for molecular entanglements

Torsional creep and creep recovery measurements have been made on a 56% polymer weight solution of an extremely high molecular weight polystyrene (M = 4.4 × 10⁷) in tri-m-tolyl phosphate and on the polymer itself after recovery both from relatively dilute and more concentrated solution in benzene by freeze drying. Although viscoelastic steady state was not achievable, an anomalously shorter rubbery plateau in the response of the bulk polymer relative to its solution was indicated. On the basis of the assumed presence of physical entanglements of the threadlike molecules, which determine the length and height of the rubbery plateau, it was predicted and confirmed that the undiluted polystyrene recovered from dilute solution would have the highest and shortest creep compliance plateau.