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91.
The carbon-fluorine bond of a trifluoromethyl group attached to a π system can be activated by metallic magnesium in the system TMSCl-THF or DMF providing a variety of difluorinated compounds via a selective CF bond cleavage. Thus, trifluoromethyl ketones, α,β-unsaturated ketones, esters, imines, and aromatics can be transformed into the corresponding difluoroenol silyl ethers, enamines, and difluoro(trimethylsilyl)methyl aromatics in good to excellent yields, respectively. This protocol enabled us to synthesize β,β-difluoroamino acids, difluoroheterocycles, and functionalized difluoroacetates. 相似文献
92.
(+)-Disparlure , and the saltmarsh caterpillar moth pheromone enantiomers were synthesized and the stereochemistry of the naturally occurring was shown to be 9, 1O. 相似文献
93.
Abstract— Photodynamic efficiency of protoporphyrin IX (PP) accumulated in HeLa cells by the incubation of PP with HeLa cells was compared with that of accumulated PP formed from 5-aminolevulinic acid (ALA) as a precursor. The ALA-induced PP was photodynamically more efficient than exogenous PP. The difference is caused by monomelic PP concentration and PP localization site in HeLa cells. Exogenous PP was accumulated mainly in plasma membrane, and the membrane was strongly damaged by irradiation. The ALA-induced PP was selectively accumulated in mitochondria and inactivated the mitochondrial function by irradiation. 相似文献
94.
Biomimetic formation of gramicidin S by dimerization-cyclization of pentapeptide precursor on solid support 总被引:1,自引:0,他引:1
The biomimetic formation of gramicidin S, cyclo(-d-Phe-Pro-Val-Orn-Leu-)2, by the dimerization and cyclization of pentapeptide precursor without the protection of δ-amino group of the Orn residue was examined on a solid support. The cyclization of H-d-Phe-Pro-Val-Orn-Leu-oxime on a resin with an oxime group of 0.62 mmol/g in 1,4-dioxane directly gave gramicidin S in a 50% yield. The dimerization-cyclization mode on the solid support was similar to that of the biosynthesis of gramicidin S on an enzyme. 相似文献
95.
Toshimasa Katagiri Yasuyuki Fujiwara Satoshi Takahashi Kenji Uneyama 《Journal of fluorine chemistry》2005,126(8):1134-1139
A structural feature of hydrogen bonding chains found in the crystals of trifluoromethylated amino alcohols is reported. Hydrogen bondings of 3-(N,N-dialkylamino)-1,1,1-trifluoro-2-propanols construct chiral spiral hydrogen bonding chains. Lone pairs on the nitrogen atoms of the amino alcohols participate in two hydrogen bondings. Detailed structural analysis of the hydrogen bonds of the 3-(N,N-dimethylamino)-1,1,1-trifluoro-2-propanol suggested that the chain built up with alternating intermolecular-medium and intramolecular-weak hydrogen bonds. The medium intermolecular hydrogen bond, which transfers a proton from the hydroxy group to the amino nitrogen, would make a tentative zwitterionic form of the molecule. Then, electrostatic attraction between the charges in the zwitterion centers induced a weak intramolecular hydrogen bond. 相似文献
96.
Kobayashi K Ishii K Sakamoto S Shirasaka T Yamaguchi K 《Journal of the American Chemical Society》2003,125(35):10615-10624
The guest- or solvent-induced assembly of a tetracarboxyl-cavitand 1 and a tetra(3-pyridyl)-cavitand 2 into a heterodimeric capsule 1.2 in a rim-to-rim fashion via four intermolecular CO(2)H.N hydrogen bonds has been investigated both in solution and in the solid state. In the (1)H NMR study, a 1:1 mixture of1a and 2a (R = (CH(2))(6)CH(3)) in CDCl(3) gave a mixture of various complicated aggregates, whereas this mixture in CDCl(2)CDCl(2) or p-xylene-d(10) exclusively produced the heterodimeric capsule 1a.2a. It was found that an appropriate 1,4-disubstituted-benzene is a suitable guest for inducing the exclusive formation of 1a.2a in CDCl(3). The ability of a guest to induce the formation of guest-encapsulating heterodimeric capsule, guest@(1a.2a), increased in the order p-ethyltoluene < 1-ethyl-4-methoxybenzene < or = 1-ethyl-4-iodobenzene < or = 1,4-dibromobenzene < 1-iodo-4-methoxybenzene < or= 1,4-dimethoxybenzene < or = 1,4-diiodobenzene. The (1)H NMR study revealed that a CH-halogen interaction between the inner protons of the methylene-bridge rims (-O-H(out)CH(in)-O-) of the 1a and 2a units and the halogen atoms of 1,4-dihalobenzenes and a CH-pi interaction between the methoxy protons of 1,4-dimethoxybenzene and the aromatic cavities of the 1a and 2a units play important roles in the formation of 1,4-dihalobenzene@(1a.2a) and 1,4-dimethoxybenzene@(1a.2a), respectively. A preliminary single-crystal X-ray diffraction analysis of guest@(1b.2b) (R = (CH(2))(2)Ph; guest = 1-iodo-4-methoxybenzene or p-xylene) confirmed that the guest encapsulated in 1b.2b is oriented with the long axis of the guest along the long axis of 1b.2b and that the iodo and the methoxy groups of the encapsulated 1-iodo-4-methoxybenzene are specifically oriented with respect to the cavities of the 2b and 1b units, respectively. 相似文献
97.
Kondo M Irie Y Shimizu Y Miyazawa M Kawaguchi H Nakamura A Naito T Maeda K Uchida F 《Inorganic chemistry》2004,43(20):6139-6141
Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1. 相似文献
98.
Ando M Takizawa M Suwabe S Yamato S Shimada K 《European journal of mass spectrometry (Chichester, England)》2003,9(6):619-622
Analysis of selenium in biological samples is very important and numerous analytical methods for the element have been developed. One of the most convenient and widely used methods for routine determination of serum selenium is a fluorometric method using 2,3-diaminonaphthalene (DAN); however, this method lacks specificity. We observed that 4,5-benzopiazselenol (BPS), a selenium derivative of DAN, is ionized with electron capture in an atmospheric pressure chemical ionization (APCI) interface, and subsequently established a method for determining total human serum selenium by means of liquid chromatography/atmospheric pressure chemical ionization mass spectrometry. All pretreatment procedures were carried out in a single test tube to minimize selenium loss. The recovery of organic or inorganic selenium spiked to human serum was 97-103%.The detection limit of BPS was equivalent to 0.2 ng of selenium and the lower quantitative limit of serum selenium was 10 ng mL(-1). The coefficient of variation of standard concentrations in control serum samples was 4.5%. The purity of the observed peak obtained from serum samples was confirmed using the ion cluster technique. 相似文献
99.
Kenji Yamamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1974,12(3):613-626
Ring-substituted phenyl propenyl ethers were found to form homopolymers without any rearrangement by metal halides. Phenyl propenyl ethers were less reactive than the corresponding phenyl vinyl ethers in cationic polymerization. In order to study the electronic effect of a substituent on the reactivity, cis-p-Cl,p-CH3, and p-CH3O-phenyl propenyl ethers were copolymerized with phenyl propenyl ether in methylene chloride at ?78°C with stannic chloride–trichloroacetic acid, and their 1H- and 13C-NMR spectra were measured. The reaction constant ρ against Hammett σp was ?2.1. The cis-phenyl propenyl ethers were slightly more reactive than the corresponding trans isomers. On the other hand, an o-methyl group decreased the reactivity of phenyl propenyl ether. The low reactivity of o-methyl phenyl propenyl ether was attributed to the steric hindrance between the propagating carbocation and the monomer. 相似文献
100.
Noriaki Nagai Mayu Kawaguchi Misa Minami Kana Matsumoto Tatsuji Sasabe Kenji Nobuhara Akira Matsubara 《Molecules (Basel, Switzerland)》2022,27(10)
N,N-diethyl-3-toluamide (DEET) is one of the most widely used insect repellents in the world. It was reported that a solution containing 6–30% cyclodextrin (CD) as a solvent instead of ethanol (EtOH) provided an enhancement of the repellent action time duration of the DEET formulation, although the high-dose CD caused stickiness. In order to overcome this shortcoming, we attempted to prepare a 10% DEET formulation using EtOH containing low-dose CDs (β-CD, 2-hydroxypropyl-β-CD (HPβCD), methyl-β-CD, and sulfobutylether-β-CD) as solvents (DEET/EtOH/CD formulations). We determined the CD concentration to be 0.1% in the DEET/EtOH/CD formulations, since the stickiness of 0.1% CDs was not felt (approximately 8 × 10−3 N). The DEET residue on the skin superficial layers was prolonged, and the drug penetration into the skin tissue was decreased by the addition of 0.1% CD. In particular, the retention time and attenuated penetration of DEET on the rat skin treated with the DEET/EtOH/HPβCD formulation was significantly higher in comparison with that of the DEET/EtOH formulation without CD. Moreover, the repellent effect of DEET was more sustained by the addition of 0.1% HPβCD in the study using Aedes albopictus. In conclusion, we found that the DEET/EtOH/HPβCD formulations reduced the skin penetration of DEET and prolonged the repellent action without stickiness. 相似文献