The polarizability of a pair of hydrogen atoms at long range

The coefficients of R^?6 and R^?9 in the long-range expansion of the parallel and perpendicular components of the polarizability of a pair of hydrogen atoms at a separation R have been calculated. The results are A⁽⁶⁾₆ = 2558.59. A⁽⁶⁾_⊥ = 1268.25, A⁽⁸⁾₆ = 90639.5 and A⁽⁸⁾_⊥ = 22010.3 au. The values of A⁽⁶⁾₆ and A⁽⁶⁾₆ and A⁽⁶⁾_| are somewhat larger than previous theoretical estimates and much larger than the classical values of 729 and 182.25 au. The terms in R^?8 arise from distortion associated with the dispersion forces and from the field of the quadrupole moment induced by the field-gradient at each atom.     

Preparation and some properties of diamine-diacid type alternating copolyamides

The polycondensations of N,N′-bis-(6-aminohexyl)oxamide, N,N′-bis-(6-aminohexyl) succinimide and N,N′-bis(6-aminohexyl)-sebacamide, with p-nitrophenyl adipate in 1,2,4-trichlorobenzene solution, using relatively low temperature (100°) to avoid the amide exchange reactions, gave alternating copolyamides corresponding to (6-6) (6-2), (6-6) (6-4) and (6-6) (6–10) nylons. These copolymers have melting points between those of their corresponding homopolyamides, whereas the random copolymers melt lower than either of the homopolymers. The microstructure of the copolymers seems to be modified by heat treatment below the melting points. Amide exchange reactions occur when they are heated to melting. C¹³ spectra allowed differentiation between the CO groups of the two constituent units of the copolymers, but not between the alternating and the random copolymers.     

Synthesis of per-6-guanidinylated cyclodextrins

Reaction of per(6-amino-6-deoxy-2,3-di-O-methyl)-α-, β- and γ-cyclodextrins with N,N′-bis(tert-butoxycarbonyl)-N″-triflylguanidine and triethylamine in tetrahydrofuran gave per[6-N,N′-bis(tert-butoxycarbonyl)guanidino-6-deoxy-2,3-di-O-methyl]-α-, β- and γ-cyclodextrins, respectively. Subsequent cleavage of the protective groups with trifluoroacetic acid in dichloromethane afforded per(6-deoxy-6-guanidino-2,3-di-O-methyl)-α-, β- and γ-cyclodextrins in very good overall yields.     

Efficient and practical synthesis of both enantiomers of 6-silyloxy-3-pyranone derivatives

Lipase catalyzed kinetic resolution of racemic cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-ol (rac)-1 was achieved in high enantiomeric excess. Transesterification of (rac)-1 with vinylacetate in ^tBuOMe yielded the alcohol (3S,6R)-1 in 99.0% ee, whereas (3R,6S)-1 was obtained, in 99.0% ee, by the lipase catalyzed ester hydrolysis of acetate (3R,6S)-2, which was obtained along with the transesterification. Both (3S,6R)-1 and (3R,6S)-1 were subjected to oxidation to provide the corresponding 6-silyloxy-3-pyranone (6R)-3 and (6S)-3, respectively. Application to the synthesis of 7, which is the key intermediate of asymmetric synthesis of pseudomonic acid A 9 is also described.     

First synthesis of 4,5-O-isopropylidene-6-thio-d-galactono-1,6-lactone as a precursor of d-galactothioseptanose

Displacement of the bromide group in methyl 6-bromo-6-deoxy-2,3:4,5-di-O-isopropylidene-d-galactonate 7, with potassium thioacetate gave methyl 6-(S)-acetyl-2,3:4,5-di-O-isopropylidene-6-thio-d-galactonate 8 in quantitative yield. Regioselective removal of the 2,3-ketal protecting group afforded methyl 6-(S)-acetyl-4,5-O-isopropylidene-6-thio-d-galactonate 11 in 70% yield. Saponification of compound 11 gave the 6-(S)-4,5-O-isopropylidene-6-thio-d-galactonic acid 12 in quantitative yield. Treatment of 12 with DIC/HOBt as coupling reagents gave, after cyclisation; the target compound: 4,5-O-isopropylidene 6-thio-d-galactono-1,6-lactone 13 in 49% yield.     

Hyperfine structure and isotope shift of some even parity levels in the YbI spectrum

Using laser induced fluorescence spectroscopy the hyperfine structure of the even parity levels 4f ¹⁴6s6d ³ D ₁, 4f ¹⁴ 6s8s ³ S ₁ and 4f ¹³ 5d6s6p (7/2, 5/2)J=1,2,3 as well as of the odd parity level 4f ¹⁴ 6s6p ³ P ₂ in neutral ytterbium has been investigated. The isotope shift of the transitions 4f ¹⁴6s6p ³ P ₀ → 4f ¹⁴ 6s6p ³ D ₁ and 4f ¹⁴ 6s6p ³ P ₂ → 4f ¹⁴ 6s8s ³ S ₁, 4f ¹³ 5d6s6p (7/2, 5/2)J=1,2,3 could be measured with high accuracy. The results for the 4f ¹⁴ 6s6p ³ D ₁ level show a considerable influence of second order effects of the hyperfine interaction. The isotope shifts of the 4f ¹⁴ 6s8s ³ S ₁ and 4f ¹³ 5d6s6p (7/2, 5/2)J=1 levels indicate a possible configuration mixing for these levels.     

Electronic structure and magnetic properties of TMRh12 clusters

We report an experimental study of energy pooling collisions involving Cs atoms in the 6P and 5D states. The 5D state was populated by a cw dye-laser tuned to the cesium dipole-forbidden transition 6S → 5D at 685.0 nm. The 6P state was populated by subsequent radiative relaxation of the 5D state. The 6P population density was determined from the absorption of a cw diode-laser probe beam. The population densities of the 5D state and the higher, by energy pooling excited states were determined by measuring the corresponding fluorescence intensities relative to the fluorescence intensity from the optically thin quasi-static wings of the cesium D ₂ line. The rate coefficient for the process Cs*(6P)+Cs*(6P)→Cs**(6D)+Cs(6S) is found to be (4.2±0.13)×10^?10 cm³ s^?1 at T=570 K. In addition, estimates of the rate coefficients for the processes Cs*(6P)+Cs*(5D)→Cs**(7D)+Cs(6S) and Cs*(5D)+ Cs*(5D)→Cs**(7F)+Cs(6S) are given.     

Ground- and excited stateg-factors of Ba+

We observed the Zeeman-splitting of the 6S _1/2-6P _1/2 resonance transition of Ba⁺ ions (493.4 nm) in a 6 T magnetic field. The ions were stored in a Penning quadrupole trap. From the splitting and the simultaneously measured cyclotron frequency of stored electrons we derived theg-factors of the 6S _1/2 and 6P _1/2 states. The results areg(6S _1/2)=2.00267(20) andg(6P _1/2)=0.66634(22).     

Hyperfine structure and multichannel quantum defect theory analysis of the 6sng rydberg series of barium

High resolution laser-atomic-beam spectroscopy has been applied to study the hyperfine structure of the barium 6sng Rydberg series forn=6?40. The singlet-triplet mixing of the two 6sng J=4 series is deduced through a diagonalisation of the total Hamiltonian. Multichannel Quantum Defect Theory (MQDT) has been used to reproduce both experimental level energies of the 6sng J=3,4 and 5 series and the extracted singlet-triplet mixing. The close-coupling channels of the 6sng Rydberg series turn out to be nearly purejj-coupled channels in contradistinction to lowerl Rydberg series. Furthermore MQDT is used to analyse the observed isotope shifts and peak intensities of the 6sng Rydberg series.     

Synthesis and regioselective substitution of C-6 alkoxy derivatives of (S)-nicotine

Enantiopure (S)-6-alkoxynicotine derivatives have been synthesized in two steps from (S)-nicotine via (S)-6-iodonicotine. Deprotonation and substitution at the C-5 position of the pyridine ring of (S)-6-methoxynicotine were achieved using mesityllithium as the base at 0 °C. Conditions for the C-4 lithiation/substitution of (S)-6-isopropoxynicotine and (S)-5-chloro-6-methoxynicotine were also developed.     

Configuration interaction effect on the hyperfine structure of the levels of the 6s6p 3 configuration in Bi II

The hyperfine structure splittings of the lines: 318.6980 nm, 328.2567 nm, 330.6264 nm, 332.7443 nm, 339.1810 nm, 340.9208 nm, 549.0347 nm, 589.8241 nm, 610.3918 nm were measured and the hyperfine structures of the levels belonging to the configuration 6s6p ³ in Bi II were determined. The influence on the hyperfine structure of the electrostatic configuration interaction between 6s6p ³ and 6s ²6pn'd configurations was discussed.     

Lifetime measurements of some TmI odd parity levels

Eleven new lifetimes of odd parity excited energy levels in four configurations: 4f ¹² 5d 6s6p, 4f ¹² 6s² 6p, 4f ¹³ 5d6s and 4f ¹³ 6s7s of atomic thulium have been mesured with atomic-beam laser spectrocopy. Two pulsed dye lasers are used for stepwise excitation and the time-resolved fluorescence decay was used to determine lifetime values. The accuracy of the measurements is about 10%.     

Magnetic properties of linear trimers in fluoride analogs of tetragonal tungsten bronze

The compounds KZnTiF₆, KZnVF₆, KVScF₆, KCrScF₆, and KMnScF₆ are fluoride analogs of Tetragonal Tungsten Bronze. M²⁺-M³⁺ ionic ordering in these fluorides provided systems which contained linear trinuclear complexes of their respective paramagnetic ions. Magnetic coupling within these linear trimers occurred below 100 K in each of the five systems. Derived magnetic susceptibility equations were fitted to observed magnetic susceptibilities for each of the possible spin systems: KZnTiF₆ (S=1/2), J/k=−114 K; KZnVF₆ (S=1), J/k=−39 K; KVScF₆ (S=3/2), J/k=−16 K; KCrScF₆ (S=2), J/k=−4 K; and KMnScF₆ (S=5/2), J/k=−7.5 K.     

New cup-shaped α-cyclodextrin derivatives and a study of their catalytic properties in oxidation reactions

A series of new α-cyclodextrin derivatives with a substituted propylene bridge attached to the 6-O's of the A,D-glucose units are reported. The compounds were prepared from the known 6^A,6^D-di-O-(prop-2-methylidene-1,3-dienyl)-hexadeca-O-benzyl-α-cyclodextrin, which was transformed into 6^A,6^D-di-O-(prop-2-methyl-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-formyl-2-hydroxy-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-aminomethyl-2-hydroxy-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-hydroxymethylidene-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-formyl-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-carboxy-1,3-dienyl)-α-cyclodextrin and 6^A,6^D-di-O-(prop-2-methoxycarbonyl-1,3-dienyl)-α-cyclodextrin. The new compounds were evaluated for their ability to affect amine and alcohol oxidations in the presence of hydrogen peroxide.     

Synthesis of all the stereoisomers of 6-methyl-2-octadecanone, 6,14-dimethyl-2-octadecanone, and 14-methyl-2-octadecanone, the components of the female-produced sex pheromone of a moth, Lyclene dharma dharma

All of the stereoisomers of the components of the female-produced sex pheromone of a moth, Lyclene dharma dharma, were synthesized. They are (R)- and (S)-6-methyl-2-octadecanone, (6R,14R)-, (6R,14S)-, (6S,14R)-, and (6S,14S)-6,14-dimethyl-2-octadecanone, and (R)- and (S)-14-methyl-2-octadecanone. Enantiomers of citronellal and methyl (S)-3-hydroxy-2-methylpropanoate were the starting materials, and olefin cross metathesis was employed as the key reaction.     

Synthesis and odor of optically active trans-2,2,6-trimethylcyclohexyl methyl ketones and their related compounds

The synthesis characterized by cationic olefin cyclizations accomplished using ketone enol esters and odor of novel (1R,6S)- and (1S,6R)-2,2,6-trimethylcyclohexyl methyl ketones (5) are described. The stereoselective syntheses of (E)-(1R,6S)- and (E)-(1S,6R)-1-(2,2,6-trimethylcyclohexyl)-2-buten-1-one (6) and (1R,6S)-ethyl 2,2,6-trimethylcyclohexylcarboxylate (7), useful raw materials for flavor and fragrance, starting from the (1R,6S)- and (1S,6R)-5 are also described.     

Two new examples of the rare C→O migration of ethoxycarbonyl groups

Two new examples of a carbon→oxygen ethoxycarbonyl group shift are described. Treatment of 3-ethoxycarbonylnitromethyl-1,2-O-isopropylidene-6-O-p-toluenesulfonyl-α-d-allofuranose (4) with Bu₄NF leads to a rearrangement to 5-O-ethoxycarbonyl-1,2-O-isopropylidene-3-nitromethyl-6-O-p-toluenesulfonyl-α-d-allofuranose (8). Similar treatment of ethyl-3-O-benzyl-6-deoxy-6-nitro-d,l-glycero-d-glucoheptofuronate (12) gives 3-O-benzyl-4-O-ethoxycarbonyl-6-deoxy-6-nitro-d-glucopyranose (16).     

Rapid configuration analysis of the solenopsins

A protocol for rapid access to the relative and absolute configurations of the solenopsins, the venom alkaloids of fire ants (Solenopsis spp.), was developed based on chiral capillary gas chromatography. The synthesis of racemic mixtures of 2-methyl-6-alkylpiperidines and the isolation of natural (2R,6R)- and (2R,6S)-2-methyl-6-undecylpiperidines allowed for the standardization of the chromatographic method. Application of this protocol revealed the previously unknown natural occurrence of four stereoisomers of 2-methyl-6-undecylpiperidine in venom samples from workers and gynes of Solenopsis saevissima.     

Absolute configurations of griseorhodins A and C

The known antibiotic and cytotoxic compounds griseorhodin A (1) and griseorhodin C (2) were produced in solid culture by Streptomyces puniceus AB10, which was isolated from the leaf-cutter ant Acromyrmex rugosus rugosus. Their absolute configurations were unambiguously established as 6S,6aR,7S,8S and 6R,6aR,7S,8R, respectively, using vibrational circular dichroism (VCD) and density functional theory (DFT) calculations.     

Crossed-second-order-effects of the isotope shift and hyperfine-structure parameters in the Eu I configuration 4f 7 6s6d

In the Eu I configuration 4f ⁷ 6s6d the isotope shift (IS) and hyperfine-structure (hfs) of the termse ⁶ D ande ¹⁰ D were determined from fourteen transitions (4f ⁷ 6s6d-4f ⁷ 6s6p) with computer supported interference spectroscopy. From the IS of altogether nine levels of 4f ⁷ 6s6d the crossed-second-order-parameterg ₃(4f,6s)=?0.90(6)mK was evaluated. The ratiog ₃/G ₃=?4.4(3)·10^?6 (G ₃: Slater Integral of the fine structure) is of the same size as that from five other independent investigations and one theoretical value. The single electron hfs splitting constantsa _4f ¹⁰ =?1.9(3)mK,a _6s ¹⁰ =391(3)mK, anda _6d ¹² =0.9(3)mK were also evaluated and are compared with those of other Eu 4f ⁷ 6snl configurations.