Cluster growth in particle-conserving cellular automata

A class of simple two-dimensional cellular automata with particle conservation is proposed for easy simulations of interacting particle systems. The automata are defined by the exchange of states of neighboring cells, depending on the configurations around the cells. By attributing an energy to a configuration of cells, we can select significant rules from the huge number of possible rules and classify them into several groups, based on the analogy with a binary alloy. By numerical calculations, cluster growth is found in two kinds of phases which reveal gas-solid coexistence and liquid droplets. Normalized scaling functions are obtained, and dynamical scaling is examined.     

Alkynylzirconation of alkynes and application to one-pot bisalkynylation of alkynes

Stereocontrolled alkynylzirconation of unactivated alkynes was achieved by the reaction of an alkyne with Cp2ZrEt2 and alkynyl halide in this order. After hydrolysis of the alkynylzirconation product, trisubstituted enyne derivatives were obtained in good yields. Functionalized enynes were also prepared by the reaction of the alkynylzirconation products with a variety of electrophiles. Subsequent addition of the second alkynyl halide to the alkynylzirconation products provided an in situ protocol for bisalkynylation of alkynes into (Z)-enediynes in good yields.     

Preparation of multisubstituted allenes from allylsilanes

[reaction: see text] A three-step route of converting allylsilanes to functionalized allenes was developed. Thermal decomposition of 1,1-dibromo-2-(silylmethyl)cyclopropanes, which were quantitatively prepared by treatment of allylsilane derivatives with CHBr3/KO(t)Bu, afforded substituted 2-bromo-1,3-butadienes with elimination of bromosilanes. The Pd-catalyzed reaction of the bromodienes with soft nucleophiles gave the allene derivatives. Previously inaccessible tri- and tetrasubstituted allenes can be prepared by this method as well.     

Unprecedented double C-C bond cleavage of a cyclopentadienyl ligand

Double C-C bond cleavage of a cyclopentadienyl ligand proceeded to titanacyclopentadienes when 2 equiv of nitriles were added and the resulting two-carbon unit and three-carbon unit were converted into a benzene derivative and a pyridine derivative, respectively, in one-pot.     

Aromatic H／D Exchange Reaction Catalyzed by Groups 5 and 6 Metal Chlorides

Groups 5 and 6 metal chlorides such as MoCl5, WCI6, NbCl5 and TaCl5 were found to be simple and very efficientcatalysts for the aromatic H/D exchange reactions. Compared with other metal chlorides such as ZnCl2, SnCl4 and TiCl4, groups 5 and 6 metal chlorides showed better catalytic activity in the H/D exchange reaction of naphthalene with C6D6. Deuteration of anthracene using MoC15 as a catalyst proceeded within 24 h at room temperature. Other aromatic compounds such as toluene, diphenylmethane and 1,1,2-triphenylethane were also deuterated smoothly in C6D6 within 24 h at room temperature.     

Selective vinyl cationic polymerization of monomers with two cationically polymerizable groups. II. p-vinylphenyl glycidyl ether: An epoxy-functionalized styrene

p-Vinylphenyl glycidyl ether (VPGE), a styrene derivative with an epoxy pendant, was polymerized by various cationic initiators, and its selective vinyl polymerization was investigated at low temperatures below ?15°C. BF₃OEt₂ (a metal halide) and CF₃SO₃H (a strong protonic acid) polymerized both vinyl and epoxy groups of VPGE, and produced cross-linked insoluble polymers. The HI/I₂ initiating system and iodine, in contrast, polymerized its vinyl group in polar solvents (CH₂Cl₂ and nitroethane) highly selectively in the temperature range of ?15 to ?40°C to give soluble polymers with a polystyrene backbone and epoxy pendants; however, under these conditions, 10–15% of the epoxy groups of the polymers were consumed during the polymerization by the reaction with the growing species. The polymerization by HI/I₂ in CH₂CI₂ involved a long-lived propagating species, as indicated by a progressive increase in the molecular weight (M?_n) of the polymers with monomer conversion and their fairly narrow molecular weight distributions (M?_w/M?_n ～ 1.6). The differences between the polymerizations of VPGE and p-isopropenylphenyl glycidyl ether, an α-methylstyrene-type counterpart of VPGE, were also discussed with an emphasis on the effects of the α-methyl group in the latter monomer.     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.     

Complete 1H and 13C NMR assignments of two phytosterols from roots of Piper nigrum

Using modern NMR techniques, including DQF-COSY, NOESY, HETCOR and HMBC, the full assignments of all 1H and 13C chemical shifts were made for stigmastane-3,6-dione and stigmast-4-ene-3,6-dione, isolated from the roots of Piper nigrum (Piperaceae). Their stereochemistry was resolved by a combination of 2D NOESY data and analysis of coupling constants. The two compounds were isolated from the genus Piper for the first time.     

On the absolute Riesz summability of orthogonal series

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