A practical synthesis of L-ribose

L-Ribose was synthesized by a simple four-step method with overall yield of 76.3% from a protected L-arabinose derivative, which is a compatible intermediate for the synthesis of L-deoxyribose. The key step of this strategy is the Swern oxidation and subsequent stereoselective reduction accompanied by inversion of the 2-hydroxy group of protected L-arabinose.     

The first halogen-substituted cyclotrigermenes: a unique halogen walk over the three-membered ring skeleton and facial stereoselectivity in the Diels-Alder reaction

Dark red crystals of the halogen-substituted cyclotrigermenes [(tBu3Si)3Ge3X; X = Cl, Br, I] were obtained in good yields by the reaction of [(tBu3Si)3Ge3]+.TTFPB- (TTFPB- = tetrakis(2,3,5,6-tetrafluorophenyl)borate) with potassium halides (KCl, KBr, or KI) in diethyl ether. The crystal structures of the halogen-substituted cyclotrigermenes reveal a cis-bent Ge=Ge double bond, caused by the introduction of the electronegative halogen atom on the sp3 germanium atom of cyclotrigermene. In solution, an intramolecular halogen migration over the three-membered ring skeleton was observed. Facial stereoselectivity in the Diels-Alder reaction of new cyclotrigermenes with 2,3-dimethyl-1,3-butadiene is also reported.     

ESR study on the reactivity of two isomers of LaC82 with disilirane

We observed photochemical and thermal addition of disilirane to the LaC₈₂-A isomer, which give new ESR active species. Both ESR spectra of the adducts in photo- and thermal reactions are well simulated by at least six octet components, and the isotropic La coupling constants and g-factors of the six octet components are determined. On the other hand, the reaction of the LaC₈₂-B isomer with disilirane gives no ESR active species. This fact is also verified by mass spectroscopic measurements. The different reactivities with disilirane of the two isomers are not interpreted by a popular view that the two isomers have a different C₈₂ cage structure, but we rather suggest that the origin of the isomers of metallofullerenes should be re-examined.     

Infrared intensities of the fundamental vibrations of liquid H2O

Infrared absorption intensities of the fundamental vibrations of liquid H₂O have been obtained by measuring transmissions at two sample thicknesses (about 9 and 0.9 μ). The effect of multiple internal reflections on the observed absorptions is examined in terms of thin-film optics. It is shown that this simple method yields precise absorption intensities, without corrections for the effects of multiple internal reflections. The resulting intensities are 89.9 × 10³ cm/mmol and 5.91 × 10³ cm/mmol for the stretching and bending vibrations, respectively. The latter value was estimated after eliminating the absorption of intermolecular vibrations from the 1400–2400 cm^-1 region by means of computer simulation.     

Molecular rheology of concentrated polymer systems. I

The primitive chain model of Doi and Edwards is generalized to include the short-time relaxation process. Stress relaxation after a sudden imposition of strain is studied in detail. It is shown that in the linear region (small strain) stress relaxation occurs in two steps, the relaxation of chain segments between the fixed entanglement points, and the relaxation of the entanglement points, in accordance with the conventional picture, whereas in the nonlinear region (large strain) there appears a new relaxation process between the above two. The characteristic time of this process is the Rouse relaxation time which the entire chain would have if there were no entanglements, and increases with the square of the molecular weight. This result is consistent with experimental observations.     

Synthesis and reactivity of β-cyclodextrin-histamine as enzyme model

Cyclodextrin (CD) has a hydrophobic cavity which acts like a binding site of an actual enzyme. But enzymatic turnover reaction did not occur in CD-catalyzed reactions. -CD was modified by a histamine group to attach a reactive functional group. -CD-histamine accelerates the hydrolysis of p-nitrophenyl acetate. Catalytic rate constant of this reaction is close to an actual enzyme, -chymotrypsin. Enzymatic turnover reaction is realized with this compound at around neutral pH value.     

Doppler-limited dye laser excitation spectroscopy of HCCl

The cw dye laser excitation spectrum of the $\text{A}\text{?}{}^1\text{A″(050) ←}\text{X}\text{?}{}^1\text{A′(000)}$ vibronic band of HCCl was observed between 16 539 and 16 656 cm^?1 with the Doppler-limited resolution, 0.03 cm^?1. The HCCl molecule was generated by the reaction of discharged CF₄ with CH₃Cl. The observed spectra were assigned to c-type transitions with ΔK_a = ±1 and also to axis-switching transitions with ΔK_a = 0 or ?2, but all with K′_a = 0, both for HC³⁵Cl and HC³⁷Cl. A rotational analysis yielded the rotational constants and quartic centrifugal distortion constants for the ground vibronic state and the band origin. A weak vibronic band, about one-third as intense as the main band, was found at about 57 cm^?1 to the violet of the main band for both isotopic species, and was ascribed to a transition from the ground vibronic state to a vibrational level, possibly (041), of the à state. The rotational levels of HC³⁵Cl in the à state showed a large perturbation; the J′ = 8, 9, and 10 levels were found to be split into two components. A normal coordinate analysis was carried out to calculate the centrifugal distortion constants and the inertia defect, which were in fair agreement with the observed values. The molecular structure of HCCl in the ground vibronic state was recalculated from the rotational constants of the two isotopic species combined with the 0.75B₀ + 0.25C₀ value previously reported for DC³⁵Cl.