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191.
The title reduction of nitroaromatics ArNO(2) by vinyl halide radical cations CH(2)[double bond]CH-X(+*)(X = Cl or Br) to form arylnitrenium ions ArNH(+) involves a change in oxidation number of nitrogen from +3 to -1. This novel reaction provides a new route for the generation of arylnitrenium ions, a highly selective method for the detection of explosives in mixtures, and offers clues to the carcinogenic activity of nitroaromatics in vivo. 相似文献
192.
Matthew S. Johnson Keith T. Kuwata Chi-Kin Wong Mitchio Okumura 《Chemical physics letters》1996,260(5-6):551-557
The infrared spectrum of the ionic cluster I−(H2O) was recorded from 3170 to 3800 cm−1 by vibrational predissociation spectroscopy. A strong multiplet observed at 3415 cm−1 and a narrow band at 3710 cm−1 were assigned as a hydrogen-bonded OH stretch and free OH stretch respectively, indicating that H2O forms a single hydrogen bond with the iodide anion. Ab initio vibrational frequencies and intensities were computed at the second-order Møller-Plesset (MP2) level for the minimum energy configuration, a nearly linear hydrogen-bonded isomer, and for a low-lying saddlepoint, a symmetric C2v bridged isomer. The spectrum predicted for the hydrogen-bonded isomer agreed well with experiment. 相似文献
193.
5, 12-Diazadibenz[a,h]anthracene ( 20 ) was synthesized in 21% overall yield for seven steps. Salient features of the synthesis include the initial, one-step conversion of trans, trans-1,4-bis-(β-nitrovinyl)benzene into 2,2″-dinitro-p-terphenyl by Diels-Alder condensation plus elimination, monocyclization of the derived 2,2″-diformylamino-p-terphenyl to give 8-(2-amino-1-phenyl)-phenanthridine ( 10 ) in the presence of fortified polyphosphoric acid, and accomplishment of a second cyclization step only after reduction of the heteroring in 10 (by means of diisobutyl-aluminum hydride) plus formylation. The 6-methyl and 6,13-dimethyl derivatives of 20 were prepared similarly. 相似文献
194.
Youngtai Yoo Larry K. Johnson Stephen N. Falling Jeremy R. Lizotte Timothy E. Long 《Journal of polymer science. Part A, Polymer chemistry》2002,40(16):2789-2798
Accelerated crosslinking of novel poly(3,4‐epoxy‐1‐butene) (3,4‐PEPB) oligomers in the presence of a cobalt‐based redox catalyst was investigated. Previous studies using model compounds, 3,4‐dimethoxy‐1‐butene and 1,4‐dimethoxy‐2‐butene, suggested that maleation of hydroxyl‐terminated 3,4‐PEPB oligomers would result in more rapid crosslinking in thin films. Novel maleated oligomers offered a unique combination of both electron‐rich and electron‐poor olefinic sites, and quantitative maleation significantly increased the crosslinking rate of 3,4‐PEPB. Efficient copolymerization between terminal maleate groups and olefinic groups in the repeating unit was proposed to account for accelerated crosslinking rates. Furthermore, the addition of novel reactive diluents, such as maleic acid mono‐ethyl ester, also effectively improved the 3,4‐PEPB crosslinking rate. Sol fraction measurements as a function of coating thickness revealed that the crosslinking rate versus oxygen diffusion was less significant for the maleated oligomers because of the presence of reactive electron‐poor olefins. Sol fractions were constant for catalyst concentrations greater than 0.25–0.50 wt % (as compared with oligomer feed). This observation suggested that a redox process was not a dominant factor in determining crosslinking rates at various experimental conditions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2789–2798, 2002 相似文献
195.
Holliday JD Rodgers SL Willett P Chen MY Mahfouf M Lawson K Mullier G 《Journal of chemical information and computer sciences》2004,44(3):894-902
This paper evaluates the use of the fuzzy k-means clustering method for the clustering of files of 2D chemical structures. Simulated property prediction experiments with the Starlist file of logP values demonstrate that use of the fuzzy k-means method can, in some cases, yield results that are superior to those obtained with the conventional k-means method and with Ward's clustering method. Clustering of several small sets of agrochemical compounds demonstrate the ability of the fuzzy k-means method to highlight multicluster membership and to identify outlier compounds, although the former can be difficult to interpret in some cases. 相似文献
196.
Argouarch G Stones G Gibson CL Kennedy AR Sherrington DC 《Organic & biomolecular chemistry》2003,1(24):4408-4417
Three chiral 2,6-disubstituted tri-N-methyl azamacrocycles have been prepared by modular methods. These macrocycles were accessed from three chiral 1,4,7-triazaheptanes intermediates that were prepared by two independent routes. The first of these routes involved the benzylamine opening of chiral tosyl aziridines followed by debenzylation but was problematic on solubility grounds. A second, more effective, route was developed which avoided debenzylation by using ammonia in the nucleophilic opening of chiral tosyl aziridines. 相似文献
197.
Reaction of Ph3GeLi with [Et4N][HFe3(CO)11] affords the new carbonylferrate salt [Et4N][Ph3GeFe(CO)4] and the same reaction provides an alternative route to the known silicon and tin analogs. Protonation of [Et4N][Ph3GeFe(CO)4] with HCl in ether-THF forms the air-sensitive, thermally rather unstable cis-Ph3GeFeH(CO)4. The latter protonates chloride ions in dichloromethane. 相似文献
198.
[reaction: see text] Stereoselective aminohydroxylation and dihydroxylation using osmium(VIII) oxidants enabled the short and efficient synthesis of the aminocyclitol core of hygromycin A. In addition to allowing the selective introduction of the heteroatoms N and O, the use of osmium (via an osmate ester) as a protecting group for a 1,2-glycol is also reported. This tactic allowed efficient differentiation of otherwise equivalent hydroxyl groups and allowed us to complete the synthesis in short order (14 steps) and excellent overall yield (12%). 相似文献
199.
E L White M S Uhrig T J Johnson B M Gordon R D Hicks M F Borgerding W M Coleman J F Elder 《Journal of chromatographic science》1990,28(8):393-399
Eight compounds from a Kentucky 1R4F reference cigarette smoke condensate have been determined by selected ion monitoring-mass spectrometry (SIM-MS) to confirm the validity of multidimensional gas chromatography (MDGC) as a quantitative tool in complex mixture analyses. Four electrostatically precipitated smoke condensate samples of 100 cigarettes each are dissolved individually in 25 mL of 2-propanol. The 2-propanol contains two methyl esters (C8 and C14) and seven deuterium-labeled compounds used as internal standards (IS). Analysis of the compounds of interest, pyridine; acetamide; acrylamide; phenol; o-, m-, and p-cresol; and quinoline, is accomplished by using two heartcuts. Heartcut times of the MDGC analysis are selected such that at least one IS is transferred with each group of compounds being analyzed. This study shows that the MDGC technique previously developed and described can be used for quantitative analyses. A comparison is made between the two types of internal standards. The results obtained for both types of internal standards agree within 20% of each other, on the average, with higher standard deviations for approximately 60% of the compounds where methyl esters are used as internal standards. 相似文献
200.
Graham DJ 《Journal of chemical information and computer sciences》2002,42(2):215-221
Information in relation to organic molecules was investigated in a previous work (Graham and Schacht, J. Chem. Inf. Comput. Sci. 2000, 40, 187). The topic is given further consideration here with the help of integer statistics. Discussed are the ramifications of an integer variable Omega(t) which quantifies the total number of binding complexions for an organic molecule. Offered is a statistical view of the maximum allowed number of independent regions D expressed by the molecule, dependent on Omega(t). We illustrate the distribution properties of D along with upper limit estimates of the regioinformation mu, also dependent on Omega(t). Integer statistics based on elementary number theory establish the key distribution properties of D and mu. In so doing, the traits distinguishing high regioinformation molecules are enumerated. The statistical approach encompasses all possible molecules and conditions, not just those reported to date in chemical databases. The aim is to view the regioinformation expressed by molecules in an alternative and general way. 相似文献