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121.
122.
Thompson RS Guler LP Nelson ED Yu YQ Kenttämaa HI 《The Journal of organic chemistry》2002,67(15):5076-5084
The 1,3-dioxolane-2-phosphenium ion, 1,3-benzodioxole-2-phosphenium ion, and o-biphenylenephosphenium ion are reported to react in a stereoselective manner with cis- and trans-1,2-diaminocyclohexanes in the gas phase in a Fourier transform ion cyclotron resonance mass spectrometer. Elimination of NH3 from an addition product was observed only for the trans isomer. Several reaction mechanisms were experimentally and computationally examined (B3LYP/6-31G(d)//HF/6-31G(d) + ZPVE level of theory). The most plausible mechanism is initiated by addition of one of the amino groups to the electrophilic phosphorus atom followed by proton transfer between the amino groups. A change to a diaxial conformation for the trans isomer facilitates anchimeric assistance by the now nucleophilic phosphorus atom as the C-N bond breaks to release NH3. Intramolecular proton transfer competes with the conformational change and ultimately leads to ethylene glycol elimination. The transition states for the critical steps of these two reactions are calculated to be nearly equal in magnitude, which rationalizes the observation of both reactions for the trans-diamine. In contrast, the adduct of the cis isomer can eliminate NH3 via a concerted 1,2-hydride shift without a need for a conformational change. However, the barrier associated with this reaction was found to be substantially greater than for proton transfer between the N- and O-atoms. The latter reaction dominates and ultimately leads to ethylene glycol elimination. 相似文献
123.
Iminodiacetate resorc[4]arene is shown to produce gels that are pH-reversible. The gels formed are clear and stable to inversion. (The gels are not stable above a certain temperature, which varies with concentration.) When the pH of an iminodiacetate resorc[4]arene solution (concentration > 7.6 mM) is lowered to below 2.5, which is near one of the Ka values of the molecule, the dissolved molecules aggregate and cause gelation of water. 1H NMR showed that at the pH of gelation a change occurs in the chemical environment of the iminodiacetate group. Scanning electron microscopy showed that the gel is composed of long strands that interweave and create a molecular mesh. 相似文献
124.
Abstract Experiments were performed to ascertain whether superoxide anion (O2 − ) was produced by the photodynamic activation of hematoporphyrin derivative (HPD). Three different systems were utilized to detect formation of O2 − , oxidation of epinephrine to adrenochrome, reduction of cytochrome c and reduction of nitro blue tetrazolium (NBT). The effects on these detectors under identical conditions for HPD + h ν were compared to those obtained with two O2 − generating systems, riboflavin + by and xanthine-xanthine oxidase, and to a singlet oxygen generating system, photoradiation of methylene blue. The results indicated that HPD + hv differed from the two O2 − generating systems in failing to reduce cytochrome c or NET, and that HPD + h ν was similar to the behavior of methylene blue + h ν . In addition, HPD + h ν but not the O2 − generating systems could inhibit mitochondrial cytochrome c oxidase activity. We conclude that the photodynamic activation of HPD does not produce O2 − as a major oxygen radical and that the effects of HPD + h ν on mitochondrial cytochrome c oxidase are not caused by O2 − . 相似文献
125.
Emtenäs H Carlsson M Pinkner JS Hultgren SJ Almqvist F 《Organic & biomolecular chemistry》2003,1(8):1308-1314
Optically active bicyclic beta-lactams were synthesized, starting from 2-H-delta 2-thiazolines and Meldrum's acid derivatives. Several methods to accomplish an ester hydrolysis without damaging the beta-lactam framework were investigated. A rapid CsOH saponification of the beta-lactam methyl esters was developed and protonation of the Cs-carboxylates by Amberlite (IR-120 H+) afforded a series of bicyclic beta-lactam carboxylic acids. Moreover, a convenient method for the synthesis of 2-H-delta 2-thiazolinecarboxylic acid methyl ester 2 was developed. Bicyclic beta-lactam carboxylic acids 7a-g and aldehydes 4a-d were screened for their affinity to the bacterial periplasmic chaperone PapD using a surface plasmon resonance technique. beta-Lactams substituted with large acyl substitutents showed better binding to the chaperone than the native C-terminal peptide PapG 8, demonstrating that bicyclic beta-lactams constitute a new class of potential bacterial chaperone inhibitors. 相似文献
126.
Garth R. Giesbrecht Gavin E. Collis John C. Gordon David L. Clark Brian L. Scott Ned J. Hardman 《Journal of organometallic chemistry》2004,689(13):2177-2185
Use of the bulky cyclopentadienyl ligand [η5-C5H2(SiMe3)3-1,2,4]− (Cp?) allows for the isolation of monomeric, mono-ring lanthanide species. As previously reported, (Cp?)K reacts with LaI3(THF)4 (THF=tetrahydrofuran) in THF/pyridine to form the mono-ring complex (Cp?)LaI2(py)3 (1) (py=pyridine); a minor product of this reaction is the bis-ring species (Cp?)2LaI(py) (2). The solid state structure of 2 reveals a monomeric compound containing a pseudo-tetrahedral metal center exhibiting no unusual intramolecular contacts. Addition of one equiv of KNHAr (Ar=2,6-iPr2C6H3) to complex 1 in THF generates the mono-anilido compound (Cp?)LaI(NHAr)(THF)2 (3), which may be converted to the more stable pyridine adduct (Cp?)LaI(NHAr)(py)2 (4) by the addition of pyridine to 3. An X-ray crystal structure of 3 indicated a trigonal bipyramidal metal center with the anilido group oriented trans to the iodide atom (N1-La1-I1=123.1(3)°). A structural study on the bis-pyridine adduct 4 revealed a similar Cs-symmetric structure with a slightly increased Nanilido-La-I angle of 132.1(2)°. Addition of KNHAr to the di-iodo bipyridine adduct (Cp?)LaI2(bipy)(py) (5), in which the two iodide atoms are cis-disposed, yields the mono-anilido complex (Cp?)LaI(NHAr)(bipy)(py) (6) (bipy=2,2′-bipyridine); this compound may also be prepared by the addition of bipy to (Cp?)LaI(NHAr)(py)2 (4). An X-ray diffraction study shows that the lanthanum center in 6 is octahedrally coordinated by a Cp? ring, an iodide, an anilido group, a pyridine molecule and two nitrogens of a bipy molecule. In this case, the anilido moiety and the iodide ligand are arranged in a cis fashion (Nanilido-La-I=111.2(2)°), resulting in a complex with C1 symmetry. Both (Cp?)LaI(NHAr)(py)2 (4) and (Cp?)LaI(NHAr)(bipy)(py) (6) are inactive as catalysts for the hydroamination/cyclization of 2-amino-hex-5-ene. 相似文献
127.
128.
Various phenylsulfonyl allene derivatives were prepared with double bonds tethered either to the alpha-position or the gamma-position of the allene. These substrates underwent a highly regio- and stereospecific thermal [2 + 2]-cycloaddition across the nonactivated cumulene double bond, forming distal cycloadducts (i.e., 57) in the case of alpha-tethered allenes and proximal adducts (i.e., 25) in the case of gamma-tethered allenes. The mechanistic rationale for the observed stereospecificity involves initial diradical formation, followed by a rapid ring closure to the more stable cis-fused ring system. The tether may be equipped with heteroatoms, allowing for the formation of fused heterocycles (e.g., 61), and the cycloaddition can be facilitated by the introduction of sterically bulky groups and/or by conformational rigidity to the tether. Other modes of cyclization were observed in the presence of sodium benzenesulfinate or Lewis acids, in which cases polar mechanisms prevail. The chemoselectivity is reversed for [4 + 2]-cycloadditions, which prefer instead to engage the vinyl sulfone moiety, independent of whether the tether is attached to the alpha- or gamma-position of the allene. 相似文献
129.
Dodds ED Kennish JM Von Hippel FA Bernhardt R Hines ME 《Analytical and bioanalytical chemistry》2004,379(5-6):881-887
The perchlorate anion (ClO
4
–
) is an anthropogenic contaminant of increasing concern in water supplies, and has been shown to disrupt thyroid activity. Most perchlorate analyses are currently carried out by ion chromatography (IC) with suppressed conductivity detection (SCD). While this procedure has been demonstrated to provide acceptable performance for analysis of water samples, the determination of perchlorate in high-conductivity aqueous extracts of plant or animal material is not readily accomplished by IC-SCD unless lengthy cleanup protocols are applied. With the addition of electrospray ionization mass spectrometry (ESI-MS) to IC, it was hypothesized that the interference imposed by various ionic species could be significantly reduced without the need for purification; however, the analysis of perchlorate in relatively unpurified extracts of biologically derived homogenates by IC-ESI-MS has not previously been described in the literature. The research presented here represents a comparison of the capabilities of IC-SCD and IC-ESI-MS to detect perchlorate in reagent water and in crude extracts of perchlorate-exposed fish (threespine stickleback, Gasterosteus aculeatus). ESI-MS was found to compare favorably to SCD for the detection of perchlorate in deionized water, and to exceed SCD performance in perchlorate analysis of fish-derived extracts. 相似文献
130.
George P. Scott Abdelaziz M. R. Elghoul 《Journal of polymer science. Part A, Polymer chemistry》1970,8(8):2255-2263
Chain-transfer constants for radicals one to five units in length were determined for the methyl acrylate–isopropanethiol system. Effects of varying ester alkyl group, mercaptan solvent and initiator on three-unit diastereomer ratio were also investigated. It was found that the proportion of syndiotactic isomer increased as the size of either the ester alkyl group or the mercaptan increased, the latter result being equivalent to a penultimate effect. Polar solvents, on the other hand, favored the formation of the isotactic form. This effect was observed in the free-radical telomerization and to an even greater degree in the base-initiated anionic telomerization. Possible reasons for solvent effects are discussed. 相似文献