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61.
[structure: see text]. All stereoisomers of a cyclic alkyne containing three helicene units, 1,12-dimethylbenzo[c]phenanthrene, are synthesized using a building block. Isomeric [3 + 3]cycloalkynes aggregate in organic solvents. Vapor pressure osmometry reveals dimer formation of (M,M,M)-[3 + 3]cycloalkynes in chloroform and benzene at concentrations above 2 mM. No higher aggregation is observed. The chirality of helicenes plays an important role in self-aggregation, and diastereomeric (M,P,M)-[3 + 3]cycloalkyne forms a dimer only above 15 mM. Aggregation of racemic (M,M,M)-[3 + 3]cycloalkyne or (M,P,M)-[3 + 3]cycloalkyne is much weaker than that of a single enantiomer. 相似文献
62.
Shigeya KobayashiYoshihiro Yamaguchi Tateaki WakamiyaYoshio Matsubara Kunihisa SugimotoZen-ichi Yoshida 《Tetrahedron letters》2003,44(7):1469-1472
Simple members of arene-azaarenecyclynes as a novel family of geometrically-controlled and shape-persistent azamacrocycles have been synthesized. Noteworthy is the specific recognition function for Sb(V). The synthesized azamacrocycles, in particular the Sb(V) complex, have unusually strong light-emitting property. 相似文献
63.
[structure: see text] New fluorescent compounds (1), lariat ethers having plural pyrenylmethyl groups on the sidearms, were prepared, and their complexation behavior with alkaline earth metal cations was examined by fluorescence spectrometry. The pyrene excimer emission decreased accompanied with an increase in the monomer emission upon complexation with the metal ion. This finding is ascribed to the cooperative participation of one of the two sidearms in the complexation of the crown ring with the metal ion. 相似文献
64.
Hidemasa Yamaguchi Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1970,8(6):1467-1479
Optically active N-bornylmaleimide (NBMI) was copolymerized with styrene, methyl methacrylate, and vinylidene chloride with a free-radical catalyst to obtain optically active copolymers. The monomer reactivity ratios for the radical copolymerization of NBMI (M2) with styrene, methyl methacrylate, and vinylidene chloride were: ST-NBMI, r1 = 0.13, r2 = 0.05; MMA-NBMI, r1 = 2.02, r2 = 0.16; VCl2-NBMI, r1 = 1.15, r2 = 0.47. The Q-e values for NBMI were Q2 = 0.48 and e2 = +1.47. The specific rotation and optical rotatory dispersion of these copolymers were measured. The correlation between the specific rotation and composition of these copolymers was not linear. The value of λc for each copolymer was independent of the copolymer composition and the comonomer, being 260 mμ for the St-NBMI system, 262 mμ for the MMA-system, and 260 mμ for the VCl2-NBMI system. The effects of solvents and temperature on the specific rotation of these copolymers were investigated. 相似文献
65.
K Sumoto M Irie N Mibu S Miyano Y Nakashima K Watanabe T Yamaguchi 《Chemical & pharmaceutical bulletin》1991,39(3):792-794
Two pyrazine derivatives [fructosazine (3) and deoxyfructosazine (6)] were simultaneously formed in a solution of D-glucosamine hydrochloride under various conditions. They showed deoxyribonucleic acid (DNA) strand breakage activity in plasmid pBR322 comparable to that of D-glucosamine. The DNA strand breakage by fructosazine (3) was stimulated by Cu2+. 相似文献
66.
Hidetake Sakuraba Yoshio Tananaka Fujio Toda 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(2):195-204
The asymmetric Michael addition of aromatic thiols to 2-cyclohexenone and maleic acid esters has been carried out by utilizing their crystalline cyclodextrin complexes suspended in water. The best chiral induction, 30% enantiomeric excess (ee), was achieved in combinations of 2-cyclohexenone and octyl maleate with the crystalline -cyclodextrin complex of benzenethiol (method A) to afford (S)-3-phenylthiocyclohexanone and (S)-octyl-2-phenylthiosuccinate, respectively, whereas the reaction of benzenethiol with 2-cyclohexenone included in -cyclodextrin (method B) inversely induced the chiral recognition to give the (R)-adduct with 4–9% ee. 相似文献
67.
S. Tamai J. Kamada T. Ono T. Kuroki K. Goto A. Yamaguchi 《Journal of polymer science. Part A, Polymer chemistry》2002,40(3):423-428
Polyimide containing an indan unit and alkyl moiety with a high molecular weight was prepared from 5,7‐diamino‐1,1,4,6‐tetramethylindan and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride. This polyimide was amorphous and soluble in common organic solvents, such as tetrahydrofuran, chloroform, and cyclopentanone. Thermogravimetry of the polyimide showed good thermal stability, indicating that a 10% weight loss of the polyimide was observed at 500 °C in nitrogen. The glass‐transition temperature of the polyimide was not observed by DSC measurement between room temperature and 400 °C at a heating rate of 10 °C/min (Apparatus: DSC3100 MAC Science Co., Ltd.). Transparency of the polyimide at 365 nm was 80%. The polyimide acted as a photosensitive resist of negative type by UV radiation. The resist had a sensitivity of 31 mJ/cm2 and a contrast of 2.3 when it was developed with cyclopentanone at room temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 423–428, 2002 相似文献
68.
Hidetake Sakuraba Toshimori Nakai Yoshio Tanaka 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):829-839
Asymmetric halogenation and hydrohalogenation oftrans-cinnamic acid have been achieved in the microcrystals of cyclodextrin complexes. The bromination of the organic acid in the cavity of -cyclodextrin gave theerythro-dibromide in 40 % optical yield which was much larger than that from the resolution treatment of the racemic dibromide with -cyclodextrin and the absolute configuration was opposite in sign. The asymmetric induction in the gas-solid reaction was not due to optical resolution but to the reaction itself which was influenced by the chiral frame of cyclodextrin. The reaction shows the molecular size effect that the acid in the cavity of -cyclodextrin reacted with smaller hydrogen bromide but did not with larger bromine and chlorine. In contrast, the guest molecule in the wider cavity of -cyclodextrin reacted with bromine and chlorine as well as hydrogen bromide. The stereospecificities of the gas-solid halogenations of the acid in -cyclodextrin were similar to those of the both reactions in the solid state and in carbon tetrachloride solution without -cyclodextrin: bromination of the acid yieldederythro-2, 3-dibromo-3-phenylpropionic acid stereospecifically in 100 % in three different conditions, but chlorination gave an excess ofthreo-2, 3-dichloro-3-phenylpropionic acid to theerythro-isomer in 7287 % yields. 相似文献
69.
The photoisomerization properties of tris(bipyridine)cobalt complexes containing six or three azobenzene moieties, namely, [Co(II)(dmAB)3](BF4)2 [dmAB = 4,4'-bis[3'-(4'-tolylazo)phenyl]-2,2'-bipyridine], [Co(III)(dmAB)3](BF4)3, [Co(II)(mAB)3](BF4)2 [mAB = 4-[3' '-(4' '-tolylazo)phenyl]-2,2'-bipyridine], and [Co(III)(dmAB)3](BF4)3, derived from the effect of gathering azobenzenes in one molecule and the effect of the cobalt(II) or cobalt(III) ion were investigated using UV-vis absorption spectroscopy, femtosecond transient spectroscopy, and 1H NMR spectroscopy. In the photostationary state of these four complexes, nearly 50% of the trans-azobenzene moieties of the Co(II) complexes were converted to the cis isomer, and nearly 10% of the trans-azobenzene moieties of the Co(III) complexes isomerized to the cis isomer, implying that the cis isomer ratio in the photostationary state upon irradiation at 365 nm is controlled not by the number of azobenzene moieties in one molecule but rather by the oxidation state of the cobalt ions. The femtosecond transient absorption spectra of the ligands and the complexes suggested that the photoexcited states of the azobenzene moieties in the Co(III) complexes were strongly deactivated by electron transfer from the azobenzene moiety to the cobalt center to form an azobenzene radical cation and a Co(II) center. The cooperation among the photochemical structural changes of six azobenzene moieties in [Co(II)(dmAB)3](BF4)2 was investigated with 1H NMR spectroscopy. The time-course change in the 1H NMR signals of the methyl protons indicated that each azobenzene moiety in [Co(II)(dmAB)3](BF4)2 isomerized to a cis isomer with a random probability of 50% and without interactions among the azobenzene moieties. 相似文献
70.
Ochiai M Suefuji T Miyamoto K Tada N Goto S Shiro M Sakamoto S Yamaguchi K 《Journal of the American Chemical Society》2003,125(3):769-773
Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10. 相似文献