Cyclic polyvanadates incorporating template transition metal cationic species: synthesis and structures of hexavanadate [PdV6O18]4-, octavanadate [Cu2V8O24]4-, and decavanadate [Ni4V10O30(OH)2(H2O)6]4-

Three types of heteropolyvanadates, [(C2H5)4N]4[PdV6O18] (1), [(C2H5)4N]4[Cu2V8O24] (2), and [(C6H5)4P]4[Ni4V10O30(OH)2(H2O)6] (3), were synthesized through the reaction between the [VO3]- anion and metal template cations of Pd(II), Cu(II), and Ni(II). The X-ray crystal structures of 1 (a = 29.952(4) A, b = 12.911(2) A, and c = 13.678(2) A, orthorhombic, space group Pca2(1) with Z = 4), 2 (a = 13.740(1) A, b = 22.488(2) A, c = 18.505(2) A, and beta= 94.058(2) degrees , monoclinic, space group P2(1)/n with Z = 4), and 3 (a = 12.333(2) A, b = 16.208(4) A, c = 16.516(3) A, alpha = 112.438(3) degrees , beta = 94.735(3) degrees , and gamma = 104.749(3) degrees , triclinic, space group P with Z = 1) demonstrate that the metal cationic species induced cyclic [VO3](n-)n (n = 6, 8, 10) ring formation and the cations are incorporated in the rings themselves. In the metal inclusion products, the cyclic vanadates act as macrocyclic ligands, in which the metal cationic species act as the templates. The cyclic vanadate is composed of tetrahedral VO4 units that share corners and incorporates a metal cationic species in the center of the molecules. The bowl-shaped complex 1 includes a Pd2+ cation that is coordinated by the oxygen donors of a boatlike hexavanadate ring. The diamagnetic complex 1 was characterized via 51V and 17O NMR spectroscopy. Complex 2 involves an octavanadate ring and two Cu2+, which are located on both sides of the mean plane as defined by the eight oxygen atoms that bridge the vanadium atoms. In the case of complex 3, the di-mu-hydroxo-bridged Ni2+ dimer with capped Ni2+ aqua ions is formed by hydrolysis to form the decavanadate ring, in which two of the tetrahedral vanadate units are not bonded to the Ni2+ core but supported by hydrogen bonds through the aqua-ligand in the capped Ni2+ cation. Complexes 1-3 in solution were clearly identified by their characteristic isotope patterns using ESI-MS studies.     

Reaction of 3,4-disubstituted 1,2,5-oxadiazole 2-oxides with dipolarophiles : Substituent and solvent effect on the reaction courses

A variety of symmetrically or unsymmetrically 3,4-disubstituttd furoxans such as dicyano, dialkyl, diacyl, bis(phenylsulfonyl), N.N'-dialkyldicarbamoyl, 3(or 4)-methyl-4(or -3)-phenyl(or nitro, ethoxy, phenoxy, phenylthio, pyrrolidinyl, phenylsulfonyl), 3(or 4)-ethyl-4(or -3)phcnyl, and 3(or 4)-ethoxy-4(or -3)-phenylsulfonylruroxan reacted with dipolarophiles in toluene or xylene at the refluxing temperature to give nitrone-type 1,3-dipolar cycloadducts, 5-substituted 1-aza-2,8-dioxabicyclo-[3.3.0]octanes and/or 3-substituted 2-isoxazoline 2-oxides. On the other hand, some of the furoxans gave 2-isoxazolines via nitrile oxide 1,3-dipolar cycloaddition in a toluene (or xylene)-DMF solvent at the refluxing temperature.     

High enantioselectivity in rhodium-catalyzed allylic alkylation of 1-substituted 2-propenyl acetates

[reaction: see text] Rhodium-catalyzed asymmetric allylic alkylation of 1-substituted 2-propenyl acetates with dimethyl malonate proceeded with high enantioselectivity in the presence of cesium carbonate as a base and a rhodium catalyst generated from Rh(dpm)(C(2)H(4))(2) (dpm = dipivaloylmethanato) and a chiral phosphino-oxazoline whose basic skeleton is axially chiral binaphthyl to give branch alkylation products in greater than 90% ee.     

Noticeable facilitation of the bismuth-mediated Barbier-type allylation of aromatic carbonyl compounds under solvent-free conditions

When milled together with bismuth shot in the presence of allyl halide, aromatic aldehydes readily underwent a Barbier-type allylation to afford the corresponding homoallyl alcohols in good yield. In contrast to the failure in solution reaction, aromatic ketones also underwent allylic carbonyl addition under solvent-free conditions to give the expected tertiary homoallyl alcohols in moderate to good yield.     

Emission of 2-phenylethanol from its β-d-glucopyranoside and the biogenesis of these compounds from [H8] l-phenylalanine in rose flowers

The hydrolysis of 2-phenylethyl β-d-glucopyranoside (3) was found to be partially inhibited by feeding with 2-phenyl-N-glucosyl-acetamidiumbromide (8), a β-glucosidase inhibitor, resulting in a decrease in the diurnal emission of 2-phenylethanol (2) from Rosa damascena Mill. flowers. Detection of [1,1,2,2′,3′,4′,5′,6′-²H₈]-2 and [1,2,2′,3′,4′,5′,6′-²H₇]-2 from R. ‘Hoh-Jun’ flowers fed with [1,1,2,2′,3′,4′,5′,6′-²H₈]-3 suggested that β-glucosidase, alcohol dehydrogenase, and reductase might be involved in scent emission. Comprehensive GC-SIM analyses revealed that [1,2,2,2′,3′,4′,5′,6′-²H₈]-2 and [1,2,2,2′,3′,4′,5′,6′-²H₈]-3 must be biosynthesized from [1,2,2,2′,3′,4′,5′6′-²H₈] l-phenylalanine ([²H₈]-1) with a retention of the deuterium atom at α-position of [²H₈]-1.     

Marstomentosides O-T polyoxypregnane glycosides from Marsdenia tomentosa

Thirteen pregnane glycosides were isolated from fresh leaves of Marsdenia tomentosa collected in the Fukuyama district. Of these, six were glycosides previously obtained from the same plant collected in the Fukuoka district and one from another Asclepiadaceous plant. The structures of the six new glycosides were determined by spectrometric method.     

Single-bubble sonochemiluminescence in aqueous luminol solutions

Sonochemiluminescence (SCL) of luminol due to a single bubble is studied through spectral measurement. No SCL was observed from a stable single bubble that emitted high-intensity sonoluminescence (SL). In contrast, SCL was observed under conditions of an unstable dancing bubble, where a bubble grows and ejects tiny bubbles, making it "dance" by counteraction. Furthermore, SCL was observed from dancing bubbles even when SL was not observed, depending on the dissolved gas content. The instability of bubble collapse is the key parameter governing SCL.     

Photoinduced ionic polymerization. III. Cationic polymerization and copolymerization of cyclohexene oxide and α-methylstyrene in the presence of pyromellitic dianhydride

The photoinduced ionic polymerization of cyclohexene oxide was studied in the presence of pyromellitic dianhydride. The polymerization is initiated by the excited chargetransfer complex between cyclohexene oxide and the electron-acceptor and proceeds by a cationic mechanism. Photoinduced cationic polymerization of α-methylstyrene was also observed in the presence of pyromellitic dianhydride. The initiation mechanism of the polymerization was elucidated by means of electron spin resonance measurements. The concentration of pyromellitic dianhydride anion-radicals measured in this way was found to be proportional to the rate of polymerization. This result shows clearly that the photopolymerization is initiated by cation-radicals formed from photoexcited donoracceptor complexes. The attempted photocopolymerization of cyclohexene oxide and α-methylstyrene gave a mixture of homopolymers. The composition of the product depends on the wavelength of the light used.     

A stannylene strategy for regioselective acylation and phosphorylation of 1,2-cyclohexylidene-myo-inositol. Its convenient resolution and phosphatidylinositol synthesis

The bis(dibutylstannylene) derivative of 1,2-cyclohexylidene-myo-inositol reacted with (S)-O-acetylmandeloyl chloride and diphosphate tetraesters to give 3,6-dimandelate and 3-phosphate, respectively. Using the stannylene methodology for the optical resolution and regioselective phosphorylation of the ketal, a concise synthesis of phosphatidylinositol with the natural configuration was accomplished.     

Preparation and characterization of high-specific-surface-area activated carbons from K2CO3-treated waste polyurethane

An activated carbon with high specific surface area was prepared from polyurethane foam by chemical activation with K2CO3 and the influences of carbonization temperature and impregnation ratio on the pore structure of the prepared activated carbon were investigated. It was found that the specific surface area of the activated carbon was at a maximum value (about 2800 m(2)/g) at a carbonization temperature of 1073 K and at an impregnation ratio of 1.0. It was concluded that the polyurethane foam structure was modified during impregnation by K2CO3, K2CO3 promoted charring during carbonization, and then the weight loss behavior was changed below 700 and above 1000 K, carbon in the char was consumed by K2CO3 reduction, and this led to the high specific surface area. The prepared activated carbon had a very sharp micropore size distribution, compared with the commercial activated carbon having high specific surface area. The amounts of three organic vapors (benzene, acetone, and octane) adsorbed on the prepared activated carbons was much larger than those on the traditional coconut shell AC and the same as those on the commercial activated carbon except for octane. We surmised that the high specific surface area was due to the modification of the carbonization behavior of polyurethane foam by K2CO3.