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11.
The reaction of ortho-alkynylated benzaldehydes 1 with allyltrimethylsilane under the Pd(OAc)2-CuCl2 catalyst system gave the isochromene derivatives 2 together with the chlorinated products 3. When the reaction was conducted in the presence of half equiv of H2O, the formation of 3 was suppressed and 2 was obtained in good to high yields. When the reaction of 1a was carried out with trimethylsilylcyanide instead of allylsilane, the cyano group-substituted isochromene 9 was obtained in 94% yield. 相似文献
12.
Masaru Asari Kumiko Oka Tomohiro Omura Chikatoshi Maseda Yoshikazu Tasaki Hiroshi Shiono Kazuo Matsubara Mitsuyoshi Matsuda Keiko Shimizu 《Electrophoresis》2013,34(3):448-455
Amplification/hybridization‐based genetic analyses using primers containing locked nucleic acids (LNAs) present many benefits. Here, we developed a novel design for universal fluorescent PCR using LNAs. Universal fluorescent PCR generates intermediate nonlabeled fragments and final fluorescent fragments in a two‐step amplification process that uses locus‐specific primers with universal tails and universal fluorescent primers. In this study, a few standard nucleotides were replaced with LNAs only in the fluorescent universal primers. The sequence of the fluorescent universal primer significantly affected the amplification efficiency. For primers with three LNAs, the fluorescent primers with stable M13(‐47) sequences provided the most efficient signal (approximately tenfold higher than the primers with M13(‐21) sequences at lower Tm values). Moreover, AT‐rich LNA substitutions in the fluorescent primers produced much lower amplification efficiencies than GC‐rich substitutions. GC‐rich LNAs produced greater differences in Tm values among primers, and resulted in the preferential production of fluorescently labeled amplicons. The specificity and sensitivity of LNA‐containing fluorescent primers were assessed by genotyping eight STRs in Japanese individuals, and full STR profiles could be generated using as little as 0.25 ng of genomic DNA. The method permitted clear discrimination of alleles and represents sensitive STR genotyping at a reduced cost. 相似文献
13.
Tetsuo Kusumoto Ken-Ichi Sato Kumiko Ogino Tamejiro Hiyama Sadao Takehara Masashi Osawa 《Liquid crystals》2013,40(3):727-732
Abstract New chiral dopants β-hydroxy ketones 1, 1,3-diols 2, 1,3-dioxanes 3 and 1,3-dioxan-2-ones 4 were designed and synthesized. Reaction of (R)-1,2-epoxyoctane with carbanions derived from 2-(4-substituted phenyl)-1,3-dithianes followed by hydrolysis of the resulting hydroxy dithianes afforded 1. Reduction of 1 gave the diols 2, which yielded 3 upon acetalization and 4 upon carbonation. The syn isomers of 2, 3, and 4 exhibited larger spontaneous polarizations, when applied as chiral dopants, than the anti isomers or hydroxy ketones 1. 相似文献
14.
Yamashita M Kamura K Yamamoto Y Akiba KY 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(13):2976-2979
A novel potential tridentate ligand, 1,8-bis(dimethylamino)-9-bromoanthracene, was synthesized. The key steps are as follows: 1) dimethylamination of 1,8-dibromo-9-methoxyanthracene by a modified Buchwald's method to afford 1,8-bis(dimethylamino)-9-methoxyanthracene, and 2) reduction of the methoxy group by LDBB (lithium di-tert-butylbiphenylide) followed by treatment with BrCF2CF2Br. The corresponding 1,8-bis(dimethylamino)-9-lithioanthracene, which should be a useful versatile tridentate ligand, could be generated by treatment of the bromide with one equivalent of nBuLi. The lithioanthracene reacted with B-chloroborane derivatives to give three 9-boryl derivatives. Although we recently reported that the crystal structure of 1,8-dimethoxy-9-B-catecholateborylanthracene was a symmetrical compound with the almost identical two O-B distances (2.379(2) and 2.441(2) A), the newly prepared 1,8-bis(dimethylamino)-9-borylanthracene derivatives clearly have unsymmetrical structures with coordination of only one NMe2 group toward the central boron atom. However, the energy difference between the unsymmetrical and symmeterical structures was found to be very small based on 1H NMR measurements, in which symmetrical anthracene patterns in the aromatic region (two kinds of doublets and a triplet) and a sharp singlet signal of the two NMe2 groups were observed even at -80 degrees C. 1,8-Bis(dimethylamino)-9-bromoanthracene itself can be a versatile ligand for transition metal compounds. In fact, direct palladation of the bromide took place by the reaction with [Pd2(dba)3].CHCl3 in THF to give the 9-palladated product. X-ray crystallographic analysis of the Pd compound showed that the square planar palladium atom was coordinated in a symmetrical fashion by both NMe2 groups (Pd-N bonds are 2.138(5) and 2.146(5) A). 相似文献
15.
Effects of organic modifiers on the chiral recognition by different types of silica-immobilized bovine serum albumin 总被引:1,自引:0,他引:1
Kumiko Harada Qun Yuan Morio Nakayama Atsushi Sugii 《Journal of chromatography. A》1996,740(2):207-213
We prepared three columns containing bovine serum albumin immobilized on silica by different means and the effects of organic modifiers in the eluent on chiral separation were studied using N-substituted amino acids. Adsorption on silica, covalent immobilization to diol-silica with carbonyldiimidazole (CSP-II) and covalent immobilization to amino-silica with glutaraldehyde were studied. CSP-II had the highest stereoselectivity and was the most affected by organic modifiers in the eluent. The hydrophobicity of amino acid moiety affected the chiral recognition of N-benzoylamino acids and the aromaticity of the N-substituted group was important. 相似文献
16.
Taisei Ueda Naoyoshi Yatsuzuka Shin‐Ichi Nagai Kumiko Okada Emi Takeichi Hiromi Segi Jinsaku Sakakibara 《Journal of heterocyclic chemistry》2001,38(1):141-145
Oxidation of 7,8‐diaminotheophylline (1) with lead tetraacetate in refluxing toluene gave a mixture of 3‐amino‐5,7‐dimethylpyrimido[4,5‐e][1,2,4]triazine‐6,8‐dione ( 2 ) and 6‐cyanoimino‐5‐diazo‐1,3‐dimethylpyrimidine‐2,4‐dione ( 4 ). The latter was transformed to 2 by the reaction with 1‐propanethiol in quantitative yield. The reaction of 4 with methanol, ethanol and 1‐propanol in the presence of rhodium ( II ) acetate gave 5‐alkoxy‐6‐(2‐alkyl‐3‐isoureido)‐1,3‐dimethylpyrimidine‐2,4‐diones ( 7a‐c ). A similar reaction of 4 with alkylamines such as n‐propylamine, n‐butylamine, isobutylamine and n‐hexylamine gave a mixture of 7‐alkyl‐8‐aminotheophyllines ( 8a‐d ) and (5‐alkylamino‐1,3‐dimethyl‐2,4‐dioxopyrimidin‐6‐yl)cyanamides ( 9a‐d ). 相似文献
17.
Chromatographic separation of styrene-methyl methacrylate (MMA) copolymers depending on the chemical composition was studied using liquefied carbon dioxide as an adsorption promoting solvent, and tetrahydrofuran, chloroform containing ethanol as a desorption promoting solvent in the mobile phase and the column packed non-bonded silica gel by a solvent gradient method. With the increase of MMA content, the elution was retarded indicating that the typical normal-phase type of adsorption occurred. The effects of type of desorption solvents, molecular mass of sample, and column temperature on the elution were investigated. 相似文献
18.
Kumiko Ohtsu Kazuhiko Ozutsumi 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):217-224
Heats of solution of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) in acetonitrile, 1,2-dichloroethane, N,N-dimethylformamide, dimethyl sulfoxide, nitromethane, propylene carbonate, pyridine and water were measured at 25 °C and the enthalpies of the transfer of 18-crown-6 from waterto the aprotic solvents were derived. The thermodynamic quantities, G1°, H1° and T S1°, for the formation of the[M(18-crown-6)]+ (M+ = Na+, K+, Rb+, Cs+, NH4
+) complexeswere determined by titration calorimetry in dimethyl sulfoxide containing0.1 mol dm-3 (C2H5)4NClO4 as a constant ionic medium at 25 °C. These thermodynamic quantities suggest that the complexationof 18-crown-6 with the alkali-metal ions mainly reflects the different solvationof 18-crown-6 and also the different degree of solvent structure. 相似文献
19.
Ohno H Takeoka Y Kadoh Y Miyamura K Tanaka T 《The Journal of organic chemistry》2004,69(13):4541-4544
Two novel palladium(0)-catalyzed cyclizations of allenenes are described. Treatment of allenenes such as N-(1-alkyl-2,3-butadienyl)-N-allylsulfonamide with an aryl halide and K(2)CO(3) in the presence of a catalytic amount of Pd(PPh(3))(4) in dioxane affords 2,3-cis-pyrrolidines in a stereoselective manner. In sharp contrast, cyclization of the same allenenes using catalytic Pd(2)(dba)(3) x CHCl(3) in the presence of allyl methyl carbonate in CH(3)CN leads to stereoselective formation of a 3-azabicyclo[3.1.0]hexane framework in moderate yields. 相似文献
20.
Calcium-induced alginate gel beads (Alg-Ca) containing various polysaccharides, including an alginate hydrolysate, were prepared and the drug release profiles were investigated. Hydrocortisone (HC) was gradually released from Alg-Ca into the mimic gastric fluid, while in intestinal fluid, it was quickly released with the dissolution of Alg-Ca. However, with Alg-Ca containing 5% chitin (CT), dissolution of Alg-Ca was not observed, and release of HC showed apparent zero-order kinetics. Furthermore, addition of the alginate hydrolysate altered the HC-release profile for Alg-Ca. 相似文献