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91.
The nucleophilic attack of hydroxylamine at the 5 position of 2-aryl-4-trifluoroacetyl-5-amino-oxazoles leads to a mixture of stereoisomeric isoxazolines. Dehydration of these isomeric isoxazolines in the presence of trifluoroacetic anhydride gives 3-amino-4-acylamino-5-trifluoromethylisoxazoles. The structures and spectroscopic data of these compounds are discussed. 相似文献
92.
Formation of Organosilicon Compounds. 89. Selective Photobromination of Si-methylated Carbosilanes A selective photobromination of the C atoms in the skeleton of Si-methylated carbosilanes is reported. (me3Si? CH2)2Sime2 reacts to me3Si? CBr2? Sime2? CH2? Sime3 in good yields (me = CH3); the second CH2 group is considerably slower brominated. Photobromination of (me2Si? CH2)3 consecutively yields a and b . Also from (me2Si? CH2)4 the derivative with one CBr2 group is accessible. Bromination of tertiary CH groups is highly preferred; this is shown by the selective formation of c . The C-bromination of SiBr-substituted carbosilanes is significantly more difficult; nevertheless (Brme2Si)2CH2 selectively forms (Brme2Si)2CBr2. Brme2Si? CH2? Sime2? CH2? Sime3 forms Brme2Si? CH2? Sime2? CBr2? Sime3, i. e., only the CH2 group non-adjacent to SiBr is attacked. The formation of CHBr groups could not be detected. Higher temperatures and longer reaction times increase the formation of polymers. 相似文献
93.
Albert Defoin Hans Fritz Christian Schmidlin Jacques Streith 《Helvetica chimica acta》1987,70(3):554-569
N-Acylnitroso derivatives 6 which were prepared by in-situ oxidation of the corresponding hydroxamic acids 5 reacted instantaneously and in high yields with dihydropyridine 4 . The Diels-Alder adducts 8 were formed regiospecifically with the acylnitroso dienophiles 6a–c , whereas the dienophiles 6d–f gave mixtures of both regioisomers 7 and 8 . These and some other results [2] were best explained by the FMO theory. The Diels-Alder adducts 7 and 8 gave the corresponding ‘anti’-cis-glycols when reacted with OsO4/N-methylmorpholine N-oxide. Hydrogenolysis of the N–O bond followed by peracetylation led to the expected aminolyxose derivatives 14 and 16 . A similar sequence, using 4 and the hydroxamic-acid derivative 18 of (+)-D-mandelic acid led, with a poor asymmetric induction, to a mixture of the expected optically active aminolyxose compounds 19A / 19B . 相似文献
94.
Summary Organic Compounds carrying groups containing both nitrogen and oxygen, such as nitro- and nitroso compounds, oximes, hydroxamic acids, azoxy compounds, and amine oxides yield nitrous acid when they are heated dry (pyrolysis). This product can be readily detected in the gas phase by theGriess nitrite reaction. This behavior provides a rapid preliminary test for members of these classes of compounds. Micro analytical limits of identification are readily obtained within the technique of spot test analysis.
Zusammenfassung Organische Verbindungen mit Stickstoff- und sauerstoffhaltigen Atomgruppen, demnach Nitro- und Nitrosoverbindungen, Oxime, Hydroxamsäuren, Azoxy verbindungen und Aminoxyde spalten bei trockenem Erhitzen (Pyrolyse) salpetrige Säure ab, die in der Gasphase durch dieGriesssche Nitritreaktion empfindlich nachweisbar ist. Dieses Verhalten ermöglicht eine schnelle Vorprüfung auf Angehörige der genannten Verbindungsklassen. In der Technik der Tüpfelanalyse werden mikroanalytische Erfassungsgrenzen erreicht.
Résumé Les combinaisons organiques porteuses d'un groupement azoté et oxygéné telles que les combinaisons nitrées et nitrosées, les oximes, les acides hydroxamiques, les composés azoxy et les oxydes d'aminés, libèrent de l'acide nitreux par chauffage à sec (pyrolyse); cet acide peut être identifié en phase gazeuse par la sensible réaction deGriess des nitrites. Ce comportement permet d'effectuer un essai préliminaire rapide sur les composés appartenant aux classes précédentes. Lorsqu'on met en oeuvre la technique de l'analyse à la touche, les limites de sensibilité atteintes permettent de travailler dans le domaine microanalytique.相似文献
95.
Formation of Organosilicon Compounds. LI. Reactions of Various Chlorinated 1.3.5-Trisilacyclohexanes with CH3MgCl and their 29SiNMR Spectra The reaction of (a) with meMgCl starts with the formation of a Grignard compound of (a) and forms (c) via (b). The reaction sequence will be described. The ring contraction of the six-membered ringsystem is also observed with compound (d) leading to (e), whereas (f) reacts to (g), the ringsystem being maintained. No ring-contraction is observed when investigating the reactions of the derivatives containing Si? H- and C? Cl-groups. Compound (i) gives rise to (j), (k) to (l) whereas cleavage occurs with (m) and (n) does not react under the conditions applied. According to the PMR and 29SiNMR spectra, the polarity of the Si? Cl-bond decreases in the compounds containing Si? Cl and CCl-groups by increasing the number of CCl2 groups. In the compounds containing Si? H and C? Cl-groups the polarity of the Si? H-bond increases with the degree of chlorination at the C-atom. By that, the different chemical behaviour can be understood. The preparations of the starting compounds are described. 相似文献
96.
The linearity of calibration curves in ion chromatography with suppressed conductivity detection using hydroxide eluents was investigated. Theoretical calibration curves were derived for strong electrolytes and weak monobasic acids and the results compared with experimental data. At low concentrations up to 1 micromol l(-1) the autoprotolysis of water induces left-curved calibration functions even for strong electrolytes like nitrate. The experimental data are best described by a quadratic function, the differences between linear and quadratic regression being up to 10%. At higher concentrations the calibration curves for strong electrolytes are linear. Due to incomplete dissociation, the calibration curves for weak mono- and dibasic acids show a right curvature. Thus, depending on the analyte and the concentration range of interest, analysts should carefully choose between a linear and a quadratic regression function. 相似文献
97.
98.
Miyagi K Sampson RW Sieber-Blum M Sieber F 《Journal of photochemistry and photobiology. B, Biology》2003,70(3):133-144
The purpose of this study was to determine in a preclinical purging model, how effective crystal violet-mediated photodynamic therapy (CV-PDT) is against solid tumor and drug-resistant mutant tumor cells, and if certain limitations of CV-PDT can be overcome by using crystal violet (CV) in combination with the membrane-active photosensitizer, Merocyanine 540 (MC540). When used under conditions that preserved an adequate fraction of normal human granulocyte/macrophage progenitors (CFU-GM), CV-PDT failed to achieve meaningful reductions of DU145 prostate, H69 small cell lung cancer, and MDA-MB-435S breast cancer cells. Melphalan-resistant L1210/L-PAM1, adriamycin-resistant P388/ADR, and adriamycin-resistant HL-60/ADR leukemia cells were markedly less sensitive to CV-PDT than their wild-type counterparts, whereas cisplatin-resistant H69/CDDP cells were more sensitive than wild-type H69 cells. Sequential exposure to MC540- and CV-PDT under conditions that preserved an adequate fraction (73% and 29%, respectively) of normal CD34-positive hematopoietic stem cells and granulocyte/macrophage progenitors was highly effective against H69 (99.997% reduction) and H69/CDDP (99.999% reduction) cells, but ineffective against HL-60/ADR, MDA-MB-435S, and DU145 cells. CV thus shows only limited promise as a single-modality purging agent. However, in certain situations, clinically meaningful tumor cell depletions can be obtained by using CV in combination with a second photosensitizer such as MC540. 相似文献
99.
Formation of Organosilicon Compounds. 70. Reactions of Si-fluorinated 1,3,5-Trisilapentanes with CH3MgCl and LiCH3 F3Si? CCl2? SiF2? CH2? SiF3 3 reacts with meMgCl. (me = Ch3 starting with a Si-methylation and not with a C-metallation as in the corresponding Si- and C-chlorinated compounds, e. g. (Cl3Si? CCl2)2SiCl2 [2]. A CCl-hydrogenation is observed too, which in the case of F3Si? CCl2? SiF2? CHCl? SiF3 4 gives meS3Si? CCl2? Sime2? CH2? Sime3. (F3Si? CCl2)2 5 reacts with meMgCl to form preferentially 1,2-Disilapropanes by cleaving a Si? Cbond. The isolation of F3Si? CCl2H and meF2Si? CCl2? SiF2me allows to locate the bond where 5 is cleaved at the beginning of the reaction. With meLi 5 reacts to form mainly me3Si? C?C? Sime3, showing that in the reaction of meLi, being a stronger reagent than meMgCl, and 5 a C-metallation occurs, following the same mechanism as in the reaction with (Cl3Si? CCl2)2)SiCl2 [2]. The reaction conditions for the synthesis of Si-fluroinated and C-chlorinated 1,3,5-Trisilapentanes in a 0.1 mol scale are reported. N.m.r. data of all investigated compounds are tabulated. 相似文献
100.
Distribution ratios are given for the extraction of gallium-(III), indium(III) and thallium(III) from aqueous solutions of hydrobromic acid into di-isopropy ether and isobutyl methyl ketone. Based on the results obtained, a scheme is presented for the quantitative separation of these elements from each other by liquid-liquid partition chromatography. The effect of a number of other metal ions upon the separation is also studied. The separation method has been applied to the analysis of a series of lead-indium alloys. 相似文献