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101.
The H2 and CH4 chemical ionization mass spectra of a series of series of substituted benzoic acids and substituted benzyl alcohols have been determined. For the benzoic acids the major fragmentation reactions of the protonated molecule involve elimination of H2O or elimination of CO2, the latter reaction involving migration of the carboxylic hydrogen to the aromatic ring. For the benzyl alcohols the major fragmentation reactions of [MH]+ involve loss of H2O or CH2O, analogous to the CO2 elimination reaction for the benzoic acids. It is shown that the CO2 and CH2O elimination reactions occur only when a conjugated aromatic ring system is present, and that for the carboxylic acid systems, methyl groups and, to a lesser extent, phenyl groups are capable of migrating. The only discernible effect of substituents on the fragmentation of [MH]+ is an enhancement of the H2O loss reaction in the benzoic acid system when an amino, hydroxyl, or halogen substituent is ortho to the carboxyl function. This ‘ortho’ effect, which differs in scope from that observed in electron impact mass spectra, is attributed to an intramolecular catalysis by the ortho substituent of the 1,3 hydrogen migration in the carbonyl protonated acid followed by H2O elimination. Apparently, this route is favoured over the direct elimination of H2O from the carbonyl protonated acid, since the latter has a high activation energy barrier because of unfavourable orbital symmetry restrictions. 相似文献
102.
Bile acids, such as cholic, chenodeoxycholic, deoxycholic, lithocholic and ursodeoxycholic acids, were allowed to react with hexafluoroisopropanol and tri-fluoracetic anhydride at 37 for 30 min. The resulting derivatives were gas chromatographed on QF-1, with flame ionization detection, and were identified by gas chromatography-mass spectrometry. Separation was good. By using this method, these acids were detected in samples of human duodenal fluid; the ratios of each were 24.4, 41.5, 24.9, 2.3 and 6.9%, respectively. 相似文献
103.
The nitro group in tertiary or secondary aliphatic nitro compounds is replaced by hydrogen or deuterium on treatment with tributyltin hydride or tributyltin deuteride, respectively. 相似文献
104.
Tanaka K Ding MY Helaleh MI Taoda H Takahashi H Hu W Hasebe K Haddad PR Fritz JS Sarzanini C 《Journal of chromatography. A》2002,956(1-2):209-214
In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent. 相似文献
105.
Hasegawa JY Takata K Miyahara T Neya S Frisch MJ Nakatsuji H 《The journal of physical chemistry. A》2005,109(14):3187-3200
Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds. 相似文献
106.
γ-Radiolysis of 5-fluorouracil and 5-fluorouridine derivatives having sulfur-containing substituents
Tokuyuki Kuroda Koji Hisamura Hiroshi Nishikawa Nobuhiro Nakamizo Yoshio Otsuji 《Journal of heterocyclic chemistry》1994,31(2):335-339
γ-Radiolysis reactions of eight 5-fluorouracil (5-FU) derivatives having sulfonyl group-containing substituents at the 1-position and five 5-fluorouridine (5-FUR) derivatives having thioureido group-containing substituents were studied under the conditions where hydrated electron (eaq?) and hydroxyl radical (HO·) become the principal reactive species. The 5-FU and 5-FUR derivatives were radiolyzed to give 5-FU and 5-FUR, respectively. The efficiency of the reactions depended upon the nature of reactive species and also upon the nature of substituents. The reactivity features of the γ-radiolysis reactions are discussed. 相似文献
107.
Chisuzu Tokoh Keiji Takabe Minoru Fujita Hiroshi Saiki 《Cellulose (London, England)》1998,5(4):249-261
Acetobacter xylinum was cultured in Hestrin-Schramm medium (control medium) and Hestrin-Schramm medium containing acetyl glucomannan (mannan medium). Loose bundles of the cellulose microfibrils are formed in the mannan medium in contrast to the normal ribbons being produced in the control medium. Rapid-freeze and substitution method followed by metal-shadowing revealed the droplet-like structures around the microfibril synthesized in the mannan medium. The cellulose synthesized in the mannan medium was stained heavily by the periodic acid-thiocarbohydrazide-silver proteinate (PATAg) method, while the cellulose synthesized in the control medium was not stained. X-ray diffractometry and FT-IR spectroscopy indicated that the addition of mannan induced a change in the crystal structure from the algal-bacterial type to the cotton-ramie type. Thus the presence of acetyl glucomannan in the medium prevents the assembly of cellulose microfibrils and changes the crystal structure of cellulose. 相似文献
108.
Acetophenone photo-sensitized addition of indene to cyclic fluoro-olefins (1,2-dichlorohexafluorocyclopentene-1, 1,2-dichlorotetrafluorocyclobutene-1 and hexafluorocyclobutene) gave the corresponding cycloadducts in satisfactory yields. The cycloadducts obtained predominantly had exo configuration.Some reactions such as reduction, oxidation, dechlorination and halogenation, of the cycloadducts were also studied. 相似文献
109.
Itsuki Shindachi Hiroshi Hanaki Ryo Sasai Tetsuya Shichi Tatsuto Yui Katsuhiko Takagi 《Research on Chemical Intermediates》2007,33(1-2):143-153
Diarylethene derivatives (DE) covalently bonded to silanol oxygens of layered silicate surfaces, i.e., magadiite (Mag), were synthesized and investigated for their photochromic behavior. The DE-Mag layered hybrids were found to undergo reversible color change by alternating UV and visible light irradiation. A more highly efficient, reproducible photochromic behavior was realized with DE-Mag than with a corresponding DE-Si possessing silyl substituents on DE in place of the Mag surface. Moreover, the present covalently bonded DE exhibited an improvement over DE hybrids incorporated in layered double hydroxide (LDH) clays, in which the repetitive photochromic behavior decreased during alternating irradiation, due to the accumulation of the photochemically inert parallel isomers of DE. 相似文献
110.
Kawasaki H Sasaki A Kawashima T Sasaki S Kakehashi R Yamashita I Fukada K Kato T Maeda H 《Langmuir : the ACS journal of surfaces and colloids》2005,21(13):5731-5737
Lyotropic phase behavior of the nonionic and the half-ionized oleyldimethylamine oxide (OlDMAO)/water systems was investigated using polarized light microscopy, small-angle X-ray diffraction, and differential scanning calorimetry. Nonionic OlDMAO formed isotropic micellar solution, nematic, hexagonal, cubic, and lamellar liquid crystalline phases as the surfactant concentration increased. In contrast, half-ionized OlDMAO (i.e., 1:1 mixture of the nonionic and the protonated species) had a greater tendency to form bilayer structures, and the phase diagram became quite similar to those of double-chained ionic surfactants rather than single-chained ones, despite the introduction of positive charges to the nonionic one. The preference of the bilayer structures in the half-ionized OlDMAO was interpreted in terms of the dimers stabilized by the hydrogen bond between the nonionic and protonated species. For alkyldimethylamine oxides with a saturated hydrocarbon chain (CnDMAO, chain length: n = 14, 16, and 18), the phase sequence of lyotropic liquid crystals was hardly affected by the protonation, but an elongation of the cylinders of the hexagonal phase was observed for the half-ionized C14DMAO. Consequently, it can be considered that the dominant bilayer formation of the half-ionized OlDMAO is attributed to the combined effect of the hydrogen-bonded dimer formation and the cis-double-bond configuration of the alkyl chain. 相似文献