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171.
William H. Donovan 《Structural chemistry》1995,6(4-5):243-254
Ab initio and semiempirical molecular orbital calculations have been applied to study the concerted and stepwise isotopic scrambling mechanisms of 2-chloroethyl methyl sulfide in the gas phase and in aqueous solution. The calculations reveal the structural details of the reactants, transition structures, and intermediates involved in this reaction and provide relative energy estimates. The concerted mechanism is found to be competitive with the stepwise mechanism in the gas phase, but the stepwise mechanism is favored in aqueous solution as no true transition structure for the concerted mechanism could be found using the solvation models. A combined approach of evaluating solvation energies with the generalized-Bom-plus-surface-tensions SM
x
solvation models of Cramer and Truhlar at ab initio optimized geometries is found to deliver the best agreement with experimentally determined reaction barriers. Together with the recent experimental results of McManus and co-workers, the present study provides insights into the controlling factors involved in the elementary reaction steps of sulfur mustards and a solid foundation for investigations into more complex reactions of related compounds. 相似文献
172.
A classical theory of dissociative attachment (DA) is developed. The DA cross section σν → DA of a molecule in the initial vibrational state ν is calculated. The model is applied to the negative ion formation in low energy electron scattering from CF3Cl molecules. Temperature effects of the DA cross section of CF3Cl can be explained within our classical model. 相似文献
173.
William H. Fink 《International journal of quantum chemistry》1973,7(6):1045-1050
The general problem of the transfer of the representation of a set of orthonormal functions from one basis to a different, nonequivalent one is considered and specialized to a matrix formulation convenient for use in molecular electronic structure calculations. A procedure is suggested for treating problems where the transfer of representation breaks into a subset of most interest and one of less interest as for example the occupied and virtual orbitals of a Hartree-Fock SCF calculation. These techniques are then applied to obtain a representation of a methyl group from an SCF wave function for methane. 相似文献
174.
Leister W Strauss K Wisnoski D Zhao Z Lindsley C 《Journal of combinatorial chemistry》2003,5(3):322-329
Solution-phase parallel synthesis has had a profound impact on the speed of compound synthesis delivering relatively pure compounds (>80%) in short order. However, to develop structure activity relationships (SAR) for a compound series, each library member should preferably be >95% pure. Historically, achieving and quantifying such high-purity criteria for each library member proved to be the slow step for most lead discovery groups. To address this issue, significant modifications have been made to a commercial Agilent preparative LC/MS system to allow for the general mass-guided purification of diverse compound libraries. The custom modifications include (1) the "DMSO slug" approach for the purification of samples with poor solubility; (2) an active splitter to reduce system back-pressure, reduce the delay volume, and allow for a variable split ratio; (3) a sample loading pump for the quick purification of large, dilute samples; (4) a preparative column-selection valve to quickly change column selectivity or sample loading; and (5) an analytical injector with a separate flow path for crude reaction or fraction analyses. 相似文献
175.
Vyskocil S Meca L Tislerová I Císarová I Polásek M Harutyunyan SR Belokon YN Stead RM Farrugia L Lockhart SC Mitchell WL Kocovský P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4633-4648
The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15-->18), followed by functional group transformations, involving C-P and C-N bond formation (18-->19 and 18-->23). Racemic intermediate 22 was resolved by co-crystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product). 相似文献
176.
The liquid Chromatographic separation of 3,3',5-triiodothyronine, 3,3',5'-triiodothyronine, and thyroxine with a nonpolar stationary phase was studied as a function of pH, temperature, organic content of the mobile phase, and ionic strength using aqueous phosphate—acetonitrile, aqueous phosphate—methanol, and aqueous phosphate— n-propanol mobile phase systems. It was demonstrated that the quality of the thyroid hormone separations, as determined by normalized peak capacity values, was unchanged with temperature, remained relatively constant with increasing ionic strength, and was affected to the greatest extent by changes in pH and organic modifier content of the mobile phase. Chromatographic behavior of the compounds studied as a function of these variables was found to be consistent with existing Chromatographic theory and/or empirical observations. Recommended conditions are aqueous phosphate—methanol mobile phase, pH 2–5 (aqueous portion), and high temperature (60–70°C). 相似文献
177.
William L. Masterton 《Journal of solution chemistry》1975,4(6):523-534
Experimental values of the salting coefficients for He, Ne, Ar, O2, and N2 in seawater are compared with values calculated from scaled-particle theory. The agreement is reasonably good; the average difference between calculated and observed values at 25°C is 0.007. Scaled-particle theory predicts correctly thatk
s should decrease as the temperature increases and that this effect should be most pronounced at low temperatures. However, the predicted magnitude ofdK
s/dt is only about half of that observed. 相似文献
178.
The disodium alkoxide of 2,6-bis(trifluoromethyl)-2,6-dihydroxy-3,3,4,4,5,5-hexafluorooxane, C(7)F(12)O(3)Na(2), 1, was prepared by reaction of the corresponding diol with MeONa in MeOH. This cyclic alkoxide readily mimics the reaction chemistry of the lithium and sodium alkoxides of perfluoropinacol. The reaction of the alkoxide 1 with covalent dichlorides and metallocene dichlorides yields a series of novel bicyclic ring systems. The crystal structure of the trioxasilane, 3, formed from (CH(3))(2)SiCl(2) was determined to provide structural information about these ring systems. Crystal data: C(9)H(6)O(3)F(12)Si, fw = 418.21 u, orthorhombic space group, Pnma (No. 62), a = 15.822(3) ?, b = 12.163(3) ?, c = 7.373(2) ?, V = 1418.9(4) ?(3), and D(calc) = 1.96 g cm(-)(3) for Z = 4 (molecule possesses mirror symmetry). Least-squares refinement on 1075 observed reflections (I > 3sigma(I)) converged with R = 0.0357 and R(w) = 0.0478. 相似文献
179.
Applied Biochemistry and Biotechnology - TheClostridium thermocellum cellulase Ss is a subunit of the extracellular cellulase complex (cellulosome). It has previously been shown that Ss hydrolyzes... 相似文献
180.
The synthesis of complexes of the type π-C5H5Mo(CO)2LX and π-C5H5Mo(CO)L2X, where XCl, Br, or I and LP(OCH2)3CR (RCH3, C2H5, or C3H7), is reported. Infrared and conductance data verified that all compounds existed as covalent species in solution. Each of the three π-C5H5Mo(CO)2LCl complexes was isolated as an inseparable mixture of cis and trans isomeric forms. Only the trans forms of the remaining π-C5H5Mo(CO)2LX complexes were observed in solution, as indicated by infrared and PMR spectra. All of the π-C5H5Mo(CO)L2X compounds apparently exist in primarily one isomeric form in solution; their PMR spectra, which exhibited a sharp triplet resonance for the ?OCH2? protons of the phosphite ligands and a single sharp π-C5H5 proton signal, indicated a predominantly trans arrangement of the phosphite ligands at room temperature. 相似文献