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101.
Robins LI Carpenter RD Fettinger JC Haddadin MJ Tinti DS Kurth MJ 《The Journal of organic chemistry》2006,71(6):2480-2485
1,2,4,5-Tetrazines (prepared from aryl nitriles) condense with isoxazolylcyclobutanones (prepared from 3-benzenesulfonyl-3-vinylcyclobutanol) in methanolic KOH to give conformationally restricted 6-isoxazol-5-yl-6,7-dihydro-5H-[1,2]diazocin-4-ones. The solution 1H NMR spectra of dihydrodiazocinone 1a with phenyl moieties at C3 and C8 reveal two conformations of the eight-membered heterocycle that are non-interconverting on the NMR time scale at ambient temperature. The kinetics of the conversion process, followed by 1H NMR between 21 and 70 degrees C in DMSO solution, yield an activation energy of approximately 21 kcal/mol relative to the kinetic conformer and show an equilibrated ratio of approximately 5:1 of the thermodynamic to the kinetic conformers. The electronic structure calculations on a model dihydrodiazocinone predict geometries for the two conformations. One of these geometries agrees with the X-ray crystallographic analysis of the thermodynamic conformation of 1a. 相似文献
102.
Purine alkylations have been plagued with formation of mixtures of N9 (usually desired), N7, and other regioisomers. We have developed methods for synthesis of 6-(azolyl)purine derivatives whose X-ray crystal structures show essentially coplanar conformations of the linked azole-purine rings. Such ring orientations position the C-H of the azole above N7 of the purine, which results in protection of N7 from alkylating agents. Treatment of 6-(2-butylimidazol-1-yl)-2-chloropurine (9) with sodium hydride in DMF followed by addition of ethyl iodide resulted in exclusive formation of 6-(2-butylimidazol-1-yl)-2-chloro-9-ethylpurine (10), whereas identical treatment of 2-chloro-6-(4,5-diphenylimidazol-1-yl)purine (11) produced a regioisomeric mixture 12/13 (N9/N7, approximately 5:1). The linked imidazole and purine rings are coplanar in 9 (the butyl side chain is extended away from the purine ring and C-H is over N7) but are rotated approximately 57 degrees in 11, and the more bulky azole substituent in 11 did not prevent formation of the minor N7 regioisomer 13. Access to various regioisomerically pure 9-alkylpurines is now readily available. 相似文献
103.
Alves GA Amato S Anjos JC Appel JA Astorga J Bracker SB Cremaldi LM Dagenhart WD Darling CL Dixon RL Errede D Fenker HC Gay C Green DR Jedicke R Karchin PE Kennedy C Kwan S Lueking LH de Mello Neto JR Metheny J Milburn RH de Miranda JM da Motta Filho H Napier A Passmore D Rafatian A dos Reis AC Ross WR Santoro AF Sheaff M Souza MH Spalding WJ Stoughton C Streetman ME Summers DJ Takach SF Wallace A Wu Z 《Physical review letters》1996,77(12):2388-2391
104.
This study examined middle school students' understanding of percent, focusing on number sense. Participants in the study were 106 seventh-grade and 93 eighth-grade students. Students were given a written test that included 21 multiple-choice questions and an open-ended item. Research interviews were conducted with 28 selected students. Students performed better interpreting a quantity expressed as a percent given a pictorial continuous region than when a pictorial discrete set of circles was given. Students had difficulty interpreting a quantity expressed as a percent of a number. The strategies used by students to make comparisons about percents represent a wide range of correct and incorrect approaches to the questions. In addition to the use of 50% and 100% as common reference points, students successfully applied fractional relationships, estimation and mental computation to make comparisons. A variety of inappropriate strategies which included computational procedures and numerical comparisons were also employed, some of which resulted in the correct multiple-choice response. 相似文献
105.
Summary The purity of the investigational antibacterial Abbott-086719.1 (I) which is 8[(3S)-3-amino-1-pyrrolidinyl]-1-cyclopropyl-7-fluoro-9-methyl-4-oxo-4H-quinolizine-3-carboxylic acid hydrochloride is determined using gradient elution HPLC. The chromatographic separation was optimized and the chromatographic parameters critical to separation are discussed in detail. Most acceptable separations were achieved using an Alltima C18 column (5 m) measuring 4.6 mm I.D.×15 cm with 0.01M–0.03M citrate eluents which were modified with acetonitrile or with mixtures of acetonitrile and methanol. Related substances in I were determinable to 0.05%. Repeatability (RSD values) for determining related substances at levels of 0.50 to 0.06% ranged from ±1.9 to ±10%. Determinations of I in 5% dextrose in water and in hydroxypropyl methylcellulose were made using the same column and a simple isocratic system. The determination of I was stability indicating with precision (RSD values) of ±0.5% to ±2.0% and good agreement with theory for formulations containing I at 1.0 to 95 mg/mL concentrations. Recoveries of I from the vehicles were quantitative and linearity of the detector response of I was demonstrated to at least 0.10 mg/mL. 相似文献
106.
107.
Vorbrüggen coupling of trimethylsilylated 2-N-acetylguanine with pentofuranose derivatives gives N7/N9 glycosyl mixtures. The N9 isomers can be obtained selectively with 2-N-acetyl-6-O-diphenylcarbamoylguanine, and even with a less reactive glucosamine derivative. 相似文献
108.
A. Gay 《The European Physical Journal C - Particles and Fields》2007,49(2):489-497
Understanding the mechanism of electroweak symmetry breaking and the origin of boson and fermion masses is among the most
pressing questions raised in contemporary particle physics. If these issues involve one (several) Higgs boson(s), a precise
measurement of all its (their) properties will be of prime importance. Among those, the Higgs coupling to matter fermions
(the Yukawa coupling). At a linear collider, the process e+e-→tt̄H will allow a direct measurement of the top-Higgs Yukawa coupling. We present a realistic feasibility study of the measurement
in the context of the TESLA collider. Four channels are studied and the analysis is repeated for several Higgs mass values
within the range 120–200 GeV/c
2.
PACS 13.66.Jn; 14.65.Ha; 14.80.Bn 相似文献
109.
The title compound was synthesized in three steps from ethoxycarbonylformamide oxime (5) and 3,4,6-tri-O-acetyl-2,5-anhydroallonyl chloride (4b) in 62% overall yield. An acid catalyzed de-esterification was required to prevent a facile base catalyzed elimination reaction. 相似文献
110.
Far infrared transmission spectra of MoCl5 homogeneously doped polyacetylene are reported. They show that in this spectral range the optical index is frequency independent but increases strongly with increasing doping level. IR conductivity is compared to d.c. conductivity. 相似文献