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101.
Tachi Y Aita K Teramae S Tani F Naruta Y Fukuzumi S Itoh S 《Inorganic chemistry》2004,43(15):4558-4560
A dicopper(I) complex supported by a novel asymmetric pentapyridine dinucleating ligand, consisting of tetradentate and tridentate metal-binding sites, has been synthesized and characterized. The dicopper(I) complex reacted with molecular oxygen at a low temperature to give an unprecedented mu-peroxo dicopper(II) complex presumably having a mu-eta1:eta2 binding mode, the spectroscopic features and the reactivity of which have been explored in detail. 相似文献
102.
103.
In the presence of a stoichiometric amount of CrCl(3) and trimethylchlorosilane (TMSCl), nucleophilic addition of arylzinc compounds 1c-h to arylaldehydes 2a,b,g smoothly proceeded at room temperature to yield corresponding benzhydrols 4a-f in good yields. From arylzinc compounds 1a,b, 3-aryl-1(3H)-isobenzofuranones 3a-f were given by the CrCl(3)-mediated reaction with arylaldehydes 2a-f. Diaryl ketones 5a-e were obtained in good yields by the addition of excess amount of benzaldehyde as an oxidant to the resulting solution after the CrCl(3)-mediated reaction between arylzinc compounds 1c-g and arylaldehydes 2b,g was completed. In the nucleophilic additions of arylzinc compounds 1a,d,f to alkyladehydes 6b-f, the treatment of arylzinc compounds with CrCl(3) was required prior to the addition of the aldehydes in order to prevent the fast protodezincation of arylzinc compounds by the enolizable aldehydes. In these CrCl(3)-mediated nucleophilic additions of arylzinc compounds to aldehydes, arylchromium(III) species are probably reactive intermediates. 相似文献
104.
Secondary carbinamines have been prepared from alkylation of N-boryl imines which were generated in situ from partial reduction of nitriles with sodium brohydride modified by carboxylic acid. 相似文献
105.
Dr. Yuichi Kobayashi Yuji Takashima Yuuya Motoyama Yukari Isogawa Kyosuke Katagiri Atsuki Tsuboi Dr. Narihito Ogawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3779-3785
The regioselectivity (r.s.) and enantiospecificity (e.s.) of the substitution reactions of secondary propargylic alcohol derivatives using reagents derived from ArMgBr and Cu salts were studied. First, the picolinate, 3-methylpicolinate, and diethylphosphonate derivatives of Ph(CH2)2CH(OH)C≡CTMS were reacted with PhMgBr/CuCN in ratios of 2.5:2.7–2.5:0.25. The use of 2.5:0.25 ratio in THF/DME (6:1) at 0 °C for 1 h afforded the α-substitution product from the phosphate with ≥98 % r.s. and 99 % e.s. CuBr⋅Me2S gave similar selectivity. The reaction system was then applied to phosphates derived from R1CH(OH)C≡CR2 and ArMgBr to obtain synthetically sufficient r.s. and e.s. values with R2=TMS, Ph, whereas iPr was borderline in terms of size as an R1 substituent. The presence of a substituent at the o-position of Ar marginally affected the selectivity. We also found that the use of PhMgBr/Cu(acac)2 in a 2:1 ratio in THF produced the γ-substitution products (allenes) with high r.s. and e.s. 相似文献
106.
Shoichi Kutsumizu Koushi Morita Tatsuya Ichikawa Shinichi Yano Shuichi Nojima Takanari Yamaguchi 《Liquid crystals》2013,40(11):1447-1458
The structure of the thermotropic cubic phases of 4′- n -alkoxy-3′-nitrobiphenyl-4-carboxylic acids (ANBC- n , where n indicates the number of carbon atoms in the alkoxy group) was studied by X-ray diffraction. For the homologues with n = 15, 16, 17, and 18, the cubic phase was of an Ia 3 d type, whereas the homologues with n = 19, 20, and 21 exhibited an Im 3 m cubic structure; for these seven homologues the same type of cubic structure was observed both on heating and cooling. Further lengthening of the alkoxy chain to n = 22 and 26, however, gave two types of cubic structure in the cubic phase region on heating, one with Im 3 m symmetry in the low temperature region and the other with Ia 3 d symmetry in the high temperature region. On cooling, the two homologues exhibited the Ia 3 d cubic structure only. This is the first example in the cubic phase region of a series of homologues containing two types of structure, dependent on temperature and n . Such a complicated phase diagram in the cubic region is clearly understood qualitatively in terms of Gibbs free energy-temperature diagrams. The dependence of structural parameters such as the cubic lattice constant on the alkoxy chain length n are also presented and discussed. 相似文献
107.
108.
Propylene was polymerized with the catalyst system (C2H5)2A1C1/ VCk/ anisole at -78°C using various conditions. The resulting polymers were successively extracted by diethyl ether, hexane, and heptane, leaving the residue. The polymers of the four series were characterized by intrinsic viscosity, gel permeation chromatography, 13C nuclear magnetic resonance, infrared spectroscopy, x-ray diffraction, and by differential scanning calorimetry. The combined evidence from the various methods indicates that this catalyst system leads to stereoblock polymers which can be fractionated according to stereochemical composition and sequence length. 相似文献
109.
Yusuke Yoshimura Ryuichiro Hibi Akiho Nakata Moeka Togashi Shoujiro Ogawa Takayuki Ishige Mamoru Satoh Fumio Nomura Tatsuya Higashi 《Biomedical chromatography : BMC》2019,33(7)
A liquid chromatography/electrospray ionization–tandem mass spectrometry‐based method was developed for the identification of the conjugation positions of the monoglucuronides of 25‐hydroxyvitamin D3 [25(OH)D3] and 24,25‐dihydroxyvitamin D3 [24,25(OH)2D3] in human urine. The method employed derivatization with 4‐(4‐dimethylaminophenyl)‐1,2,4‐triazoline‐3,5‐dione to convert the glucuronides into fragmentable derivatives, which provided useful product ions for identifying the conjugation positions during the MS/MS. The derivatization also enhanced the assay sensitivity and specificity for urine sample analysis. The positional isomeric monoglucuronides, 25(OH)D3‐3‐ and ‐25‐glucuronides, or 24,25(OH)2D3‐3‐, ‐24‐ and ‐25‐glucuronides, were completely separated from each other under the optimized LC conditions. Using this method, the conjugation positions were successfully determined to be the C3 and C24 positions for the glucuronidated 25(OH)D3 and 24,25(OH)2D3, respectively. The 3‐glucuronide was not present for 24,25(OH)2D3, unlike 25(OH)D3, thus we found that selective glucuronidation occurs at the C24‐hydroxy group for 24,25(OH)2D3. 相似文献
110.