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An automatic method for the absolute determination of total sulfur, which overcomes the tendency of previous methods to give low sulfur recoveries on samples with high oxygen demand, is described. The technique combusts the sample in oxygen and sweeps the combustion gases through a hydrogen peroxide trap to remove the sulfur oxides from the gas stream. The trap contents are volatilized and swept with nitrogen through reduced copper heated to 890 °C. Sulfur oxides are quantitatively converted to sulfur dioxide and titrated coulometrically with iodine. Halogens are held by the copper and do not interfere with the sulfur determination. Analysis time is 12 min and automation of the method allows unattended operation. Sample size is 0.5 to 20 mg. Sulfur levels of 0.05 to 100% can be determined. 相似文献
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Deerenberg S Schrekker HS van Strijdonck GP Kamer PC van Leeuwen PW Fraanje J Goubitz K 《The Journal of organic chemistry》2000,65(16):4810-4817
A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities. 相似文献
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The rearrangement of 3a,4,5,6-tetrahydrosuccinimido[3,4-b]acenaphthen-10-one and two methylated derivatives using Schmidt conditions is described. The ratio of the major product, 2,3,8,9-tetrahydro-3-oxo-1H-benz[de]isoquinoline-1,9a-(7H)dicarboximide, to the minor product, 2,3,6,7-tetrahydro-3-oxo-4H-benz[ij]-isoquinoline-4,4a-(5H)dicarboximide, under different acidic conditions is given. The ratios of analogous products from the methylated derivatives are similar under similar conditions. 相似文献
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Evans PA Sawyer JR Lai KW Huffman JC 《Chemical communications (Cambridge, England)》2005,(31):3971-3973
The crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. 相似文献
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Chisholm MH Macintosh AM Huffman JC Wu D Davidson ER Clark RJ Firth S 《Inorganic chemistry》2000,39(16):3544-3550
Mo2(OtBu)6 and Mo2(NMe2)6 each react with (S,S,S)-triisopropanolamine (2 equiv) in benzene to yield dimolybdenum bis((S,S,S)-isopropanolaminate(3-)), Mo2[(OC-(S)-HMeCH2)3N]2 (M identical to M), as a blue crystalline solid. Cell parameters at -160 degrees C: a = 17.389(6) A, b = 10.843(3) A, c = 10.463(3) A, beta = 125.28(1) degrees, Z = 2 in space group C2. The molecular structure involves an Mo2 unit inside an O6N2 distorted cubic box. The Mo2 axis is disordered about three positions with occupancy factors of ca. 45%, 45%, and 10%. Despite this disorder, the molecular structure is shown to contain a central Mo identical to Mo unit of distance 2.15(3) A coordinated to two triolate ligands which each have two chelating arms and one that spans the Mo identical to Mo bond. The local Mo2O6N2 moiety has approximate C2h symmetry, and the Mo-N distances are long, 2.4 A. The 1H and 13C(1H) NMR spectra recorded in benzene-d6 are consistent with the geometry found in the solid-state structure. The blue color arises from weak absorptions, epsilon approximately 150 dm3 mol-1 cm-1, at 580 and 450 nm in the visible region of the electronic absorption spectrum. Raman spectra recorded in KCl reveal pronounced resonance effects with excitation wavelengths of 488.0, 514.5, and 568.2 nm, particularly for the 322 cm-1 band, which can probably be assigned to nu(Mo identical to Mo). The electronic structure of this compound is investigated by B3LYP DFT calculations, and a comparison is made with the more typical ethane-like (D3d) Mo2(OR)6 compounds is presented. The distortion imposed on the molecule by the triisopropanolaminate(3-) ligands removes the degeneracy of the M-M pi molecular orbitals. The HOMO and SHOMO are both M-M pi and M-O sigma* in character, while the LUMO is M-M pi* and the SLUMO is predominantly M-O sigma* with metal sp character. The calculated singlet-singlet transition energies are compared with those implicit in the observed electronic spectrum. 相似文献
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