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991.
The effect of certain aromatic compounds on the PMR spectrum of methyl methacrylate (MMA) was investigated. The magnitude of observed aromatic-induced shifts decreased in the order benzene ? styrene > chlorobenzene ≈ bromobenzene.Assuming that the interaction arises from a stoichiometric 1:1 complex, equilibrium parameters for the MMA-benzene interaction have been estimated. ΔH ± S.E. (ΔH) = ?(8 ± 4) kJ mol?1. These effects are likely to have a small influence on the kinetics of copolymerization with aromatic monomers and polymerization in aromatic solvent. The stereochemistry of the solute-solvent interactions suggests that MMA takes a cis-conformation in solution, which is relevant to the mechanism of stereoregular polymerizations of this monomer. 相似文献
992.
Methoxy groups exert an activating and ortho/para directing influence in light induced nucleophilic substitution reactions (cyanation, hydroxylation, etc) of aromatic compounds in aqueous media. The first chemical step in these processes is monophotonic ionization of the aromatic compound in its lowest triplet state, followed by reaction of the radical cation with the nucleophile Quantum yields of photocyanation of 4-fluoro- and 4-chloroanisole indicate that in 99% (mole fraction) water virtually all triplets formed undergo electron ejection.This hypothesis is in agreement with the results of charge density calculations for the radical cations. It is directly supported by the similarity of the product composition of these photochemical substitutions with that of anodic substitutions, where the intermediacy of an aromatic cation is generally accepted. The presence of an oxidizing agent (oxygen, or persulphate) is required only when a hydrogen is replaced. The nucleophilic photosubstitution at electron rich aromatic systems in solvents as water can therefore be classified as an Sr+n1(3Ar*) process. 相似文献
993.
M. G. Voronkov O. M. Trofimova Yu. I. Bolgova L. V. Klyba L. I. Larina A. I. Albanov V. A. Pestunovich N. F. Chernov K. B. Petrushenko 《Chemistry of Heterocyclic Compounds》2003,39(12):1639-1644
We have synthesized 1- and 2-(trimethylsilylmethyl)- and 1- and 2-(trimethoxysilylmethyl)benzotriazoles by reaction of 1,2,3-benzotriazolylsodium with trimethyl- or trimethoxy(chloromethyl)silane. We obtained 1- and 2-(silatranylmethyl)benzotriazoles by transesterification of the latter with triethanolamine. 相似文献
994.
Tokuyama R Takahashi Y Tomita Y Suzuki T Yoshida T Iwasaki N Kado N Okezaki E Nagata O 《Chemical & pharmaceutical bulletin》2001,49(4):347-352
A structure-activity relationship (SAR) study on 5-substituted oxazolidinones as an antibacterial agent is described. The oxazolidinones, of which 5-acetylaminomethyl moiety was converted into other functions, were prepared and evaluated for antibacterial activity. Elongation of the methylene chain (8) and conversion of the acetamido moiety into guanidino moiety (12) decreased the antibacterial activity. The replacement of carbonyl oxygen (=O) by thiocarbonyl sulfur (=S) enhanced in vitro antibacterial activity. Especially, compound 16, which had the 5-thiourea group, showed 4-8 stronger in vitro activity than linezolid. Our SAR study revealed that the antibacterial activity was greatly affected by the conversion of 5-substituent. 相似文献
995.
The neutral polysaccharides of the tuberous roots ofBiebersteinia multifida consist of three weakly branched glucans, A, B, and C. It has been established by periodate and chromic acid oxidation, methylation, and mass spectrometry that in the chains of glucans A, B, and C the monosaccharides are linked to one another by -1 6 bonds and there is branching at the C-3 atoms of the glucopyranose residues.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 188–191, March–April, 1993. 相似文献
996.
B. Slootmaekers A.C. Fabretti H.O. Desseyn R. Vochten S.P. Perlepes 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1996,52(14):1883-1896
In this article, the preparation, X-ray powder results and vibrational properties of a new type of complex with planar dithiooxamides are discussed. In acetonitrile, Cu(I) can form complexes with the formula Cu(LH2)2X1 (X = Cl, Br) where LH2 is an N,N'-disubstituted dithiooxamide. Complexes with N,N'-dimethyldithiooxamide and N,N'-diethyldithiooxamide have been prepared. A thorough vibrational analysis with infrared and Raman techniques was performed, assisted by H/D and 63Cu/65Cu isotope substitution. The vibrational study indicates the presence of an inversion centre in the structure. This leads to the proposal of a very unusual six-coordinate structure for these compounds, with the two dithiooxamide ligands, having S-cis conformation, coordinated to the same copper and with the halogens bridged between two different copper atoms. Confirmation of this result was attempted by X-ray analysis, but although several methods were tried to obtain crystals, only powder X-ray data could be obtained, which could not give a definitive answer. Since such six-coordinate Cu(I) has never been described before, a less rigourous interpretation of the vibrational data was followed, leading to a square-pyramidal five-coordinate structure, with a rather weak bond between Cu(I) and a terminal halogen. The latter structure, with the data available up to now, seems a bit more likely, since five-coordination for Cu(I) has already been described. 相似文献
997.
An organic-phase biosensor based on paraffin/graphite modified with sweet potato (Ipomoea batatas (L.) Lam.) tissue as the source of peroxidase was developed and used for determining hydroquinone in cosmetic creams. This enzyme in the presence of hydrogen peroxide catalyses the oxidation of hydroquinone to p-quinone which electrochemical reduction back to hydroquinone was obtained at a peak potential of -0.22 V. The recovery of hydroquinone from two samples ranged from 99.1 to 104.1% and a rectilinear analytical curve for hydroquinone concentration from 7.5x10(-5) to 1.6x10(-3) M (r=0.9991) were obtained. The detection limit was 8.1x10(-6) M and relative standard deviation was <1.0% for a solution containing 7.3x10(-4) M hydroquinone and 1.0x10(-3) M hydrogen peroxide in 0.10 M tetrabutylammonium bromide methanol-phosphate buffer solution (95:5% v/v) (n=10). The results obtained for hydroquinone in cosmetic creams using the proposed biosensor are in close agreement with those obtained using a Pharmacopoeia procedure at the 95% confidence level. 相似文献
998.
D. Kreisle K. Leiter O. Echt T. D. Märk 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1986,3(2):319-322
Multiply charged ammonia cluster ions are produced by adiabatic nozzle expansion and subsequent ionization by electron impact. They are analyzed in a double focussing sector field mass spectrometer (reversed geometry). Doubly charged clusters are only detected above a critical size of 51 and triply charged clusters above 121. Some of these multiply charged ions decay via metastable dissociation processes in the experimental time window accessible. Doubly charged ammonia clusters with sizes ofn≧51 lose one neutral monomer or, roughly ten times less probable, two neutral monomers. Conversely, triply charged ammonia clusters with sizes 110≦n≦120 show an extremely asymmetric Coulomb dissociation resulting in doubly charged cluster ions of about 90% of the initial mass 相似文献
999.
E. P. Lokshin O. A. Tareeva T. G. Kashulina 《Russian Journal of Applied Chemistry》2007,80(8):1275-1280
Solubility of yttrium, praseodymium, neodymium, and gadolinium sulfates in the presence of sodium and potassium ions and the composition of solid phases were studied at 20°C in relation to the concentration of acids in sulfuric acid, phosphoric acid, and sulfuric-phosphoric acid solutions containing up to 36 wt % H2SO4 and 33.12 g 1?1 H3PO4. 相似文献
1000.
V. L. Klimov G. A. Bergman O. K. Karlina 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2006,80(11):1816-1818
It was shown that the published data on the thermodynamic properties of aluminum monooxycarbide Al2OC (ed) are not consistent with the phase diagram of the Al2O3-Al4C3 system. A thermodynamic modeling of the equilibrium state of the Al2O3-Al4C3 system made it possible to obtain new estimates of the standard entropy and enthalpy of formation of aluminum monooxycarbide: S°(298.15 K, cd. Al2OC) = 45.3 J/(K mol) and Δf H°(298.15 K, cd, Al2OC) = ?625.6 kJ/mol. 相似文献