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41.
Tomio Shimizu Yoshiyuki Hayashi Takehiro Taniguchi Kazuhiro Teramura 《Tetrahedron》1985,41(4):727-738
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. 相似文献
42.
Highly fluorescent polymer particles were prepared with Eu beta-diketonates complex as a fluorophore by miniemulsion polymerization technique. Eu beta-diketonates complex has a long decay time, a large Stokes shift, and very narrow emission bands in comparison with other organic fluorescent compounds. Aqueous miniemulsion was prepared by mixing monomer, crosslinker, hydrophobe, and Eu beta-diketonates complex and then putting the mixture into an aqueous solution of surfactant, followed by ultrasonication. An aqueous solution of initiator was added to the miniemulsion to obtain fluorescent polymer particles, which were monodispersed without aggregation. Particle size was decreased to deca-nano scale by increasing the amount of surfactant. Fluorescent intensity was increased by using Eu beta-complex coordinated with additional ligand. Further fluorescence quantum yields and fluorescent properties in the presence of DNA were investigated to the confirm superiority of Eu beta-diketonates complexes in polymer particles. 相似文献
43.
Synthesis of 12-deoxyroyleanone, cryptoquinone, 11,14-dihydroxy-8,11,13-abietatrien-7-one, and related derivatives from dehydroabietic acid 总被引:1,自引:0,他引:1
Yoh-ichi Matsushita Yoshihisa Iwakiri Satoru Yoshida Kazuhiro Sugamoto Takanao Matsui 《Tetrahedron letters》2005,46(21):3629-3632
Naturally occurring abietane quinones and hydroquinone, namely, 12-deoxyroyleanone (1a), cryptoquinone (4a), and 11,14-dihydroxyabieta-8,11,13-trien-7-one (5a), together with the epimers of tryptoquinones D (2) and F (3), were first synthesized from dehydroabietic acid (6). 相似文献
44.
Kazuhiro Kobayashi Hiroyasu Takeuchi Shinzo Seko Yoshikazu Kanno Sachiko Kujime Hiroshi Suginome 《Helvetica chimica acta》1993,76(8):2942-2950
The 2,3-dihydro-1H-benz[f]indole-4,9-diones 3a–d , h were formed in a one-step reaction in 13–82% yield by an unprecedented [3 + 2] regioselective photoaddition of 2-amino-1,4-naphthoquinone ( 1 ) with various electronrich alkenes 2 (Scheme 1, Table). The [3 + 2] photoadducts derived from 1 with vinyl ethers and vinyl acetate gave 1H-benz[f]indole-4,9-diones 4e , f , i , in 33–72% yield, by spontaneous loss of the corresponding alcohol or AcOH from the resulting adducts; 4i has a kinamycin skeleton. The [3 + 2] photoaddition also took place on irradiation of the differently substituted amino-1,4-benzoquinones 6 , 7 , and 12 and excess alkenes 2 in benzene, giving 1H-indole-4,7-dione derivatives 13 and 14 (Scheme 3), 15a and 16 (Scheme 4), and 18 (Scheme 4), respectively. The initial products in these photoadditions were proved to be hydroquinones, the air oxidation of which yielded the heterocyclic quinones; 2,3-dihydro-2-methoxy-2-methyl-5-phenyl-1H-indole-1,4,7-triyl triacetate ( 19 ) was isolated after treatment of the crude photoaddition mixture obtained from 2-amino-5-phenyl-1,4-benzoquinone ( 7 ) and 2-methoxyprop-1-ene ( 2f ) with Ac2O and pyridine under N2. A pathway leading to the annelated hydroquinones involving ionic intermediates arising from an electron transfer in these photoadditions is proposed (Scheme 5). 相似文献
45.
Uehara K Hikichi S Inagaki A Akita M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2788-2809
A series of dinuclear complexes, [Tp(R)M--M'L(n)] [Tp(iPr(2) )M--Co(CO)(4) (1; M=Ni, Co, Fe, Mn); Tp(#)M--Co(CO)(4) (1'; M=Ni, Co); Tp(#)Ni--RuCp(CO)(2) (3')] (Tp(iPr(2) )=hydrotris(3,5-diisopropylpyrazolyl)borato; Tp(#) (Tp(Me(2),4-Br))=hydrotris(3,5-dimethyl-4-bromopyrazolyl)borato), has been prepared by treatment of the cationic complexes [Tp(iPr(2) )M(NCMe)(3)]PF(6) or the halo complexes [Tp(#)M--X] with the appropriate metalates. Spectroscopic and crystallographic characterization of 1-3' reveals that the tetrahedral, high-spin Tp(R)M fragment and the coordinatively saturated carbonyl-metal fragment (M'L(n)) are connected only by a metal-metal interaction and, thus, the dinuclear complexes belong to a unique class of xenophilic complexes. The metal-metal interaction in the xenophilic complexes is polarized, as revealed by their nu(CO) vibrations and structural features, which fall between those of reference complexes: covalently bonded species [R--M'L(n)] and ionic species [M'L(n)](-). Unrestricted DFT calculations for the model complexes [Tp(H(2) )Ni--Co(CO)(4)], [Tp(H(2) )Ni--Co(CO)(3)(PH(3))], and [Tp(H(2) )Ni--RuCp(CO)(2)] prove that the two metal centers are held together not by covalent interactions, but by electrostatic attractions. In other words, the obtained xenophilic complexes can be regarded as carbonylmetalates, in which the cationic counterpart interacts with the metal center rather than the oxygen atom of the carbonyl ligand. The xenophilic complexes show divergent reactivity dependent on the properties of donor molecules. Hard (N and O donors) and soft donors (P and C donors) attack the Tp(R)M part and the ML(n) moiety, respectively. The selectivity has been interpreted in terms of the hard-soft theory, and the reactions of the high-spin species 1-3' with singlet donor molecules should involve a spin-crossover process. 相似文献
46.
We found that Br-/Br3- is more suitable than an I-/I3- couple in dye-sensitized solar cells in terms of higher open-circuit photovoltage (Voc) production and higher overall energy conversion efficiency (eta) if the dye sensitizer has a more positive potential than that of Br-/Br3-. Under simulated AM1.5 one sun, an eosin Y dye-sensitized solar cell containing 0.4 M LiBr + 0.04 M Br2 electrolyte in acetonitrile yielded a short-circuit photocurrent (Jsc) of 4.63 mA cm(-2), Voc of 0.813 V, and fill factor (FF) of 0.693, corresponding to 2.61% of eta. Under the same conditions except for the electrolyte 0.4 M LiI + 0.04 M I2 in acetonitrile instead, the device produced 1.67% of eta (Jsc = 5.15 mA cm(-2), Voc = 0.451 V, FF = 0.721). Replacement of I-/I3- with Br-/Br3- in eosin Y dye-sensitized solar cells yielded a significant increase in Voc offset by slight decreases in Jsc and FF, leading to an increase in eta by 56%. The significant gain in Voc was attributed to the enlarged energy level difference between the redox potential of the electrolyte and the Fermi level of TiO2 and the suppressed charge recombination as well. The rate for charge recombination between bromine and the injected electrons was determined to be first order in bromine. 相似文献
47.
Takashi Yokoyama Kazuhiro Ikemoto Takatsugu Kihara Kouhei Teramura Keisuke Uryu Kohji Shimizu Motoki Bitoh Kohji Matsuzaki Michio Zenki 《Journal of solution chemistry》2006,35(5):639-657
Coordination equilibrium constants (K
NiS) of some donor solvent molecules to 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecanenickel(II) ([Ni(Me4[12]aneN4)]2+) were determined in nitrobenzene (a noncoordinating bulk solvent). The first (K
NiS1) and second stepwise coordination equilibrium constants (K
NiS2) for 1,4,7,10-tetraazacyclododecanenickel(II) ([Ni([12]aneN4)]2+), 1,4,8,11-tetraazac yclotetradecane- nickel(II) ([Ni([14] aneN4)]2+), 1,4,8,11-tetrathiacyclotetra-decanenickel(II) ([Ni([14]aneS4)]2+) were also reinvestigated. The K
NiS values for [Ni(Me4[12]aneN4)]2+ were compared to those of [Ni([12]aneN4)]2+, (1R,4S, 8R,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) (R,S,R,S-[Ni(Me4[14]aneN4)]2+), R,R,S,S-[Ni(Me4[14]aneN4)]2+, [Ni([14]aneN4)]2+, and [Ni([14]aneS4)]2+. Coordination of pyridine (Py), N,N,N′,N′-tetramethylurea (TMU), and N,N-dimethylacetamide (DMA) to [Ni(Me4[12]aneN4)]2+ was observed, although these donor solvent molecules did not coordinate to R,S,R,S-[Ni(Me4[14]aneN4)]2+. The K
NiS values for Py, TMU, and DMA are 7.9, 2.8, and 9.0 dm3⋅mol−1, respectively. Some hydrogen-bonding waters were coordinated to R,S,R,S-[Ni(Me4[14]aneN4)]2+, but such waters did not coordinate to [Ni(Me4[12] aneN4)]2+. Also, the K
NiS2 values were larger than the corresponding K
NiS1 values for [Ni([14]aneS4)]2+. Furthermore, the K
NiS1 values for [Ni([12]aneN4)]2+ were the largest among these nickel(II) complex cations. The K
NiS, K
NiS1, and K
NiS2 values are discussed in terms of properties of the donor solvents and steric strains of these nickel(II) complex cations. 相似文献
48.
Yamada K Yagishita S Tanaka H Tohyama K Adachi K Kaizaki S Kumagai H Inoue K Kitaura R Chang HC Kitagawa S Kawata S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(11):2647-2660
Novel metal-complex assemblies constructed from the flexible hinge-like ligand H(2)bhnq (H(2)bhnq=2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq(2-) ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq(2-) in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq(2-) ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq(2-) ion. 相似文献
49.
Akira Matsumoto Yutaka Kukimoto Kazuhiro Aoki Masayoshi Oiwa 《Journal of polymer science. Part A, Polymer chemistry》1983,21(12):3493-3502
Seven glycol bis(allyl phthalate)s (GBAP) and four glycol bis(allyl succinate)s (GBASu) as reactive oligomers were prepared and their polymerization behaviors were investigated in detail in terms of cyclopolymerization and gelation as compared with diallyl dicarboxylates. Thus, the rates of polymerization of GBAPs were reduced compared to diallyl phthalate, being attributed to the steric effect on the intermolecular propagation of the uncyclized radical, whereas those of GBASus were enhanced as a consequence of intermolecular association by dipole–dipole interaction in polar GBASu monomers. Cyclization was enhanced in the following order: diallyl aliphatic dicarboxylates series < GBASu series < GBAP series. Gelation was discussed according to Gordon's theory; the actual gel-point conversions increased with an increase in the molecular weight of monomers, although the discrepancy between actual and theoretical gel-point conversion inversely tended to be decreased. The decreased delay in gelation with an increase of the molecular weight of monomers is ascribed to the reduction of excluded volume effects on crosslinking. 相似文献
50.
Sensitive, reactive, and hydrophilic fluorogenic reagents for thiols with the benzofurazan skeleton, 4-(N-acetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (AcABD-F) and 4-(N-trichloroacetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (TCAcABD-F) have been developed. These reagents reacted with thiols within 10 min at 60 degrees C. AcABD-F and TCAcABD-F themselves do not fluoresce but are strongly fluorescent after the reaction with thiol compounds. The generated derivatives were highly water-soluble, since they dissociated a proton and ionized in the neutral pH region. The derivatives with four biologically important thiol compounds were separated on a reversed-phase HPLC column and detected fluorometrically at 504 nm with excitation at 388 nm. The detection limit attained for homocysteine with AcABD-F was 25 fmol on column (11 nM) (signal-to-noise ratio = 3), and that for glutathione with TCAcABD-F was 45 fmol on column (20 nM). 相似文献