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21.
Although pentamethylene sulfide (tetrahydrothiopyran) lacks acidic hydrogen, OsVIII has been found to catalyze its oxidation by alkaline K3Fe(CN)6 to produce 3-hydroxypentamethylene sulfide as the only product. The kinetics reveal first-order dependence on ferricyanide and OsVIII, and zero order on pentamethylene sulfide and OH–. The effects of introduced electrolytes, K4Fe(CN)6, relative permittivity and temperature have also been studied. On the basis of kinetic evidence, a mechanism that involves anation of the osmium catalyst (sulfide/water interchange) followed by intramolecular proton abstraction, followed by an electron transfer step has been proposed and discussed. 相似文献
22.
The aim of this paper is to present two different approachs in order to obtain an existence result to the so-called quadrature
surface free boundary problem. The first one requires the shape derivative calculus while the second one depends strongly
on the compatibility condition of the Neumann problem. A necessary and sufficient condition of existences is given in the
radial case. 相似文献
23.
Heterometallic molecular chromium wheels are fascinating new magnetic materials. We reexamine the available experimental susceptibility data on MCr7 wheels in terms of a simple isotropic Heisenberg Hamiltonian for M=Fe, Ni, Cu, and Zn and find in that FeCr7 needs to be described with an iron–chromium exchange that is different from all other cases. In a second step we model the behavior of the proton spin lattice relaxation rate as a function of applied magnetic field for low temperatures as it is measured in nuclear magnetic resonance (NMR) experiments. It appears that CuCr7 and NiCr7 show an unexpectedly reduced relaxation rate at certain level crossings. 相似文献
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An electrolytic device for decomposition of water has been developed which readily gives hydrogen and oxygen for isotopic measurement with a mass spectrometer. A 20-mul sample can be decomposed quantitatively in 10 min with good reproducibility. The results produced are comparable with those obtained by reduction with uranium. 相似文献
28.
M.Iqbal Choudhary SyedGhulam Musharraf Amtul Sami Atta‐ur‐Rahman 《Helvetica chimica acta》2004,87(10):2685-2694
The microbial transformation of (?)‐Ambrox® ( 1 ), a perfumery sesquiterpene, by a number of fungi, by means of standard two‐stage‐fermentation technique, afforded ambrox‐1α‐ol ( 2 ), ambrox‐1α,11α‐diol ( 3 ), ambrox‐1α,6α‐diol ( 4 ), ambrox‐1α,6α,11α‐triol ( 5 ), ambrox‐3‐one ( 6 ), ambrox‐3β‐ol ( 7 ), ambrox‐3β,6β‐diol ( 8 ), 13,14,15,16‐tetranorlabdane‐3,8,12‐triol ( 9 ), and sclareolide ( 10 ) (Schemes 1 and 2). Further incubation of compound 10 with Cunninghamella elegans afforded 3‐oxosclareolide ( 11 ), 3β‐hydroxysclareolide ( 12 ), 2α‐hydroxysclareolide ( 13 ), 2α,3β‐dihydroxysclareolide ( 14 ), 1α,3β‐dihydroxysclareolide ( 15 ), and 3β‐hydroxy‐8‐episclareolide ( 16 ) (Scheme 3). Metabolites 2 – 5, 12, 13 , and 16 were found to be new compounds. The major transformations include a reaction path involving hydroxylation, ether‐bond cleavage and inversion of configuration. Metabolites 11 – 16 of sclareolide showed significant phytotoxicity (Table 1). The structures of the metabolites were characterized on the basis of spectroscopic techniques. 相似文献
29.
Boruah A Rao IN Nandy JP Kumar SK Kunwar AC Iqbal J 《The Journal of organic chemistry》2003,68(12):5006-5008
A cis-proline derived cyclic mimic of a type VI beta-turn is synthesized via a ring-closing metathesis reaction. The solution NMR conformational study indicates that the major conformer of the cyclic peptide adopts a type VIa beta-turn in CDCl(3) and a type VIb beta-turn in DMSO-d(6). 相似文献
30.
Acetates derived from the adducts of the Baylis-Hillman reaction can be reacted in a regioselective manner with amines in the presence of palladium(0) catalyst to afford alpha-dehydro-beta-amino esters (2 and 3) in good yields. The regioselectivity of the reaction can be controlled by temperature and reaction medium leading to the synthesis of regioisomers 2 or 3. The alpha-dehydro-beta-amino acid 3 is a turn inducer, and the dipeptides 6 derived from it show the presence of an eight-membered intramolecular hydrogen bond. Also, cobalt(II) chloride catalyzes the cleavage of epoxy peptides with alpha-dehydro-beta-amino acid derivative 3b to afford the corresponding dipeptide derivatives 8, which exhibit an intramolecular hydrogen bond and thus mimic a beta-turn. This intramolecular hydrogen bonding preorganizes the corresponding diallylated peptide 8c for cyclization via ring-closing metathesis to afford the cyclic peptide 9 as a constrained mimic of a beta-turn. 相似文献