Saturated heterocycles, 162 [1]. synthesis and steric structures of 3,4-disubstituted 1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones

The reaction of 1-(hydrazidomethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 3 with aromatic aldehydes yield hydrazones 4a,b or pyrimido[6,1-a]isoquinolines 5a-c depending upon the proportions of the reagents. With ketones, 3 gives only hydrazones 4a-d and 7 , which can be transformed to pyrimidoisoquinolines 10a-e and 11 with aldehydes. The ring closures are stereospecific; the relative configurations were determined by DNOE measurements.     

LC Enantioseparation of β-Lactam and β-Amino Acid Stereoisomers and a Comparison of Macrocyclic Glycopeptide- and β-Cyclodextrin-Based Columns

Direct reversed-phase high-performance liquid chromatographic methods were developed for the separation of the enantiomers of tricyclic β-lactams, cis-3,4-benzo-6-azabicyclo[3.2.0]heptan-7-one, cis-4,5-benzo-7-azabicyclo[4.2.0]-octan-8-one, cis-5,6-benzo-8-azabicyclo[5.2.0]nonan-9-one and new bicyclic β-amino acids, the six- and seven-membered homologues of cis-1-amino-4,5-benzocyclopentane-2-carboxylic acid (benzocispentacin), cis-1-amino-5,6-benzocyclohexane-2-carboxylic acid and cis-1-amino-6,7-benzocycloheptane-2-carboxylic acid. The direct separations of the analytes were performed on chiral stationary phase (CSP) columns containing the macrocyclic glycopeptide antibiotic teicoplanin (Chirobiotic T), teicoplanin aglycone (Chirobiotic TAG), vancomycin (Chirobiotic V), vancomycin aglycone (Chirobiotic VAG), ristocetin A (Chirobiotic R) or a new dimethylphenyl carbamate-derivatized β-cyclodextrin-based Cyclobond DMP. The results achieved with the different methods were compared in systematic chromatographic examinations. The effects of an organic modifier and of the mobile phase composition on the separation and the separation efficiency of different columns were investigated. The difference in enantioselective free energy between the aglycone CSP and the teicoplanin CSP for these β-lactams and β-amino acids ranged between 0.3 and −1.1 kJmol⁻¹. Better enantioseparations were attained in most cases on the aglycone CSP.

     

Stereochemical studies, 47, saturated heterocycles, 25 a simple stereospecific synthesis of oxazasteroids

8-Aza-12-oxasteroids have been synthesized in a simple three-step process. As a consequence of two stareocontrolled reactions, the product is a stereospecifically homogeneous isomer with all-$\text{trans}$ ring junctions; its structure has been determined by ¹H and ¹³C NMR spectroscopy and X-ray diffraction.     

Electron delocalization and dimerization in solid C59N doped C60 fullerene

Electron spin resonance and ab initio electronic structure calculations show an intricate relation between molecular rotation and chemical bonding in the dilute solid solution. The unpaired electron of C59N is delocalized over several C60 molecules above 700 K, while at lower temperatures it remains localized within short range. The data suggest that below 350 K rigid C59N-C60 heterodimers are formed in thermodynamic equilibrium with dissociated rotating molecules. The structural fluctuations between heterodimers and dissociated molecules are accompanied by simultaneous electron spin transfer between C60 and C59N molecules. The calculation confirms that in the C59N-C60 heterodimer the spin density resides mostly on the C60 moiety, while it is almost entirely on C59N in the dissociated case.     

Electronic effects of heterocyclic ring systems as evaluated with the aid of 13C and 15N NMR chemical shifts and NBO analysis

The electronic effects of the 5‐ and 6‐membered heterocyclic rings on the C?N? N unit of five different hydrazone derivatives of pyridine‐2‐, ‐3‐ and ‐4‐carbaldehydes, pyrrole‐2‐carbaldehyde, furan‐2‐ and ‐3‐carbaldehydes and thiophene‐2‐ and ‐3‐carbaldehydes have been studied with the aid of ¹³C and ¹⁵N NMR measurements together with the natural bond orbital (NBO) analysis. As model compounds are used the corresponding substituted benzaldehyde derivatives. The polarization of the C?N unit of the hydrazone functionality of the heteroaryl derivatives occurs in an analogous manner with that of phenyl derivatives. The electron‐withdrawing heteroaryl groups destabilize and the electron‐donating groups stabilize the positive charge development at the C?N carbon while the effect on the negative charge development is opposite. The ¹⁵N NMR chemical shift of the C?N and C?N? N nitrogens and the NBO charges at C?N? N unit can be correlated with the replacement substituent constants σ of the heteroaryl groups. ¹³C NMR shifts of the C?N carbon of N,N‐dialkylhydrazones of the heteroarenecarbaldehydes can be correlated with a dual parameter equation possessing the polar substituent constant σ* of the heteroaryl group and the electronegativity of the heteroatom as variables. Copyright © 2008 John Wiley & Sons, Ltd.     

Stopping power of low-energy deuterons in 3He gas

The stopping power of atomic and molecular deuterons in ³He gas was measured over the range E _d = 10 to 100 keV using the ³He pressure dependence of the ³He(d,p) ⁴He reaction yield. At energies above 30 keV, the observed stopping power values are in good agreement with a standard compilation. However, near 18 keV the experimental values drop by a factor 50 below the extrapolated values of the compilation. In a simple model, the behavior is due to the minimum 1s↦2s electron excitation of the He target atoms (= 19.8 eV, corresponding to E _d = 18.2 keV), i.e. it is a quantum effect, by which the atoms become nearly transparent for the ions.     

Shaping of picosecond pulses for pumping optical parametric amplification

The use of temporally shaped pump pulses for optical parametric chirped-pulse amplification can increase the efficiency and suppress possible spectral distortions in this process. With this goal in mind a novel method for shaping narrowband picosecond pulses has been developed. The method is based on the pulse stacking principle, where replicas of the incoming pulse are created in a specially designed four-beam interferometer. The replicas are recombined with appropriate relative delays. The interferometer design allows for a unique flexibility in varying the pulse shape, since all relevant degrees of freedom, such as relative intensities and delays between the pulse replicas are independently adjustable. Here we describe the design of our device in detail and report on the experimental demonstration of its pulse-shaping capabilities. PACS 42.65.Yj; 42.65.Re; 42.81.Gs     

Internal magnetic fields in submicron particles of barium hexaferrite detected by 57Fe NMR

⁵⁷Fe nuclear magnetic resonance (NMR) spectra of hexaferrite BaFe₁₂O₁₉ powder samples prepared by glass crystallization method were measured at 4.2 K and analyzed in comparison to spectra of single crystals. Samples with various mean particle dimensions were tested. NMR spectral lines corresponding to individual iron sublattices showed pronounced frequency shifts of their positions and a significant line broadening compared to single crystals. The significant contribution to the line shifts and line shape had a uniform macroscopic origin giving identical absolute value of shifts and the same line shapes for all measured lines of a particular sample. Estimations of demagnetization fields based on mean particle dimensions reasonably corresponded to the observed frequency shifts for particle mean diameter 67 nm, or had a higher value for a sample with mean diameter of 340 nm, for which a presence of domain walls was detected by NMR. In the spectrum of a sample with the smallest particles (～16 nm), an additional contribution having broader lines and faster spin-spin relaxations was found. It could be assigned to weaker exchange interactions or deviations of magnetic moment directions from the hexagonal axis in a surface layer.