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991.
[C(4)H(3)N(CH(2)NMe(2))-2]AlMe(2) (1) is prepared in 88% yield by the reaction of substituted pyrrole [C(4)H(4)N(CH(2)NMe(2))-2] with 1 equiv of AlMe(3) in methylene chloride. Reaction of compound 1 with 1 equiv of phenyl isocyanate in toluene generates a seven-membered cycloaluminum compound [C(4)H(3)N[CH(2)NPh(CONMe(2))]-2] AlMe(2) (2). The phenyl isocyanate was inserted into the aluminum and dimethylamino nitrogen bond and induced an unusual rearrangement which results in C-N bond breaking and formation. A control experiment shows that the reaction of substituted pyrrole [C(4)H(4)N(CH(2)NMe(2))-2] with 1 equiv of phenyl isocyanate in diethyl ether yields a pyrrolyl attached urea derivative [C(4)H(3)N(CH(2)NMe(2))-2-[C(=O)NHPh]-1] (3). The demethanation reaction of AlMe(3) with 1 equiv of 3 in methylene chloride at 0 degrees C afforded O-bounded and N-bounded aluminum dimethyl compounds [C(4)H(3)N(CH(2)NMe(2))-2-[C(=O)NPh]-1]AlMe(2) (4a) and [C(4)H(3)N(CH(2)NMe(2))-2-[CO(=NPh)]-1]AlMe(2) (4b) in a total 78% yield after recrystallization. Both 4a and 4b are observed in (1)H NMR spectra; however, the relative ratio of 4a and 4b depends on the solvent used. Two equivalents of AlMe(3) was reacted with 3 in methylene chloride to yield a dinuclear aluminum compound AlMe(3)[C(4)H(3)N(CH(2)NMe(2))-2-[C(=O)NPh]-1] AlMe(2) (5). Reaction of 5 with another equivalent of ligand 3 results in the re-formation of compounds 4a and 4b. 相似文献
992.
Introductionlnthcstud}ofmcthaneoxidativccoupIing(0CM),aseriesofcatalystshavebeendevelopedandox}'genspeciesoncatal}'stst"ereinvestigatedextensively.Alotofpapershavebeenpublishedonthisarea.Anongkindsof0CMcatalystsmetalhalidespromotedmctaloxides.cspcciall}'Li /Mg0catal}'stl1~3l.havcbecnmostoftenstudied.Themostpromisingindustrialoncshavebeenthoughttoberarcearthoxidesbasedcatalysts.H.L.Wanelajl#Ihavesuccessfull\'madeuseofmetalfluoridesin0CM,andfoundthebcttcrpron1otingcffectofmctalfluoridcstomc… 相似文献
993.
It A proposed that the M-cluster cage (Kim-Rees model) in active N2-ase can exert shape-selective molecular-sieve effects in molecular recognition of exogenous substrates, by providing inside multinuclear active-sites the cavity for N2, C2H2, cyclopropene, and N2O reduction, with [Mo-3Fe]-site available only for N2 reduction: on the other handn-RC— CH,n-RC— N,n-RN-C , C—N– and N3
–, are bound outside the cavity at the [2Fe]-site left by the labilizable ligand Y. A terminal carboxylate of the Mo-bound (R)-homocitrate is just in position to protect a H2-evolution site on the P-cluster pair from CO inhibition, and also to take part in mediating a P-cluster-to-Mo-site H+-relay system (involving two hydrogen-bonded H2O) specifically required for N. reduction. The nonreducibility of CO at the [Mo-3Fe]-site is also explained. Experimental support for molecular-sieve effects of M-cluster cage has been obtained from the observed decrease in ethene-cis-d: selectivity by competitive inhibition of HC—CH reduction in D2O by N—N.Dedicated to Jiaxi Lu on the occasion of his 80th birthday. 相似文献
994.
Harold Rosenberg Tsu-Tzu Tsai Ngoc Kim Ngo 《Journal of polymer science. Part A, Polymer chemistry》1982,20(1):1-13
A method for the first synthesis of high molecular weight carbonate-containing siloxanylene polymers was successfully developed. The procedure covered the preparation and polymerization of pure carbonate-containing bis-silanols which included bis(4-hydroxydimethylsilylphenyl)-carbonate, bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)-phenyl] carbonate, and their meta analogs. Because conventional siloxane polymerization methods, such as the heterocondensation of bis-silanols with diaminosilanes or homocondensation reactions catalyzed by alkali reagents, decomposed carbonate linkages, a new polymerization technique that involved the use of phosgene was used. The procedure was both facile and effective in the polymerization of other arylene bis-silanols. 相似文献
995.
Tsu T. Tsai Fred E. Arnold Wen F. Hwang 《Journal of polymer science. Part A, Polymer chemistry》1989,27(9):2839-2848
A series of novel ABA block copolymers were synthesized containing a rigid-rod (B) block for reinforcement and a flexible coil (A) block as the matrix. Poly[(benzo[1, 2d: 4, 5d′]bisthiazole-2,6-diyl)-1,4-phenylene] (PBT) was the rigid-rod (B) block utilized in this study and was polymerized in such a way as to provide carboxylic acid end-groups. The carboxy-terminated PBT was copolymerized with the AB monomers, 3,4-diaminobenzoic acid and 4-amino-3-mercaptobenzoic acid, which generates a benzimidazole or benzthiazole (A) block, as well as grafts the blocks together. Composition of the blocks could be varied by the weight of AB monomer used in the copolymerizations. Solution behavior of the copolymers in methanesulfonic acid was determined, and fibers were obtained by wet spinning techniques. The block copolymers exhibited typical tenacities of 200 ksi, 16 Msi modulus, and an elongation to break of 1.4%. Critical concentration values for fabrication increased approximately 3% over mechanical mixtures of the same heterocyclic components. 相似文献
996.
Pinacol -1-trimethylsilyl-1-propene-3-boronate reacts with aldehydes to form (±)-(*,*)-3-trimethylsilyl-4-hydroxy-1-alkenes, which can be deoxysilylated stereoselectively to either 98% or 99% 1,3-dienes, including the separate components of the red bollworm moth pheromone. 相似文献
997.
A rapid, sensitive method for the determination of morphine and amphetamine was developed using capillary zone electrophoresis coupled with electrospray interface (ESI), ion-trap tandem mass spectrometry (CE-ESI-MS2). Morphine and amphetamine were separated in 20 mM ammonium acetate buffer (pH 6.6) and detected by ion-trap mass detector in different analytical time segments (0-6.25 min for amphetamine and 6.25-12.0 min for morphine) in which the tune file for each compound was used separately. Molecular ions of morphine (m/z 286) and amphetamine (m/z 136) were detected at 5.77 and 6.83 min, respectively, while product ions of MS2 for each compound (m/z 229, 201 for morphine and m/z 119 for amphetamine) were detected almost exactly at the same time with their parent compounds. The limits of detection (LOD) for MS2 determination were 30 and 50 ng/mL for amphetamine and morphine, respectively, with an S/N ratio of 3. For more sensitive detection of morphine, the sample was injected for a longer time (i.e., 80 s) and hydrodynamically transported into a CE capillary for MS detection. Morphine and its product ion appear at 0.36 and 0.39 min on the ion chromatogram, respectively, with a five-fold increase of detection sensitivity (LOD, 10 ng/mL). The CE-MS system thus established was further applied for forensic urine samples screened as morphine-positive by fluorescence polarization immunoassay (FPIA). These results indicated the feasibility of CE-ESI-MS2 for confirmative testing of morphine in urine sample. 相似文献
998.
[reaction: see text] This Mg-TiCl4-promoted CH2-transfer reaction of CH2Cl2 represents an extremely simple, practical, and efficient methylenation of a variety of ketones and aldehydes, especially in enolizable or sterically hindered ketones such as 2,2-dimethylcyclohexanone, camphor, and fenchone. 相似文献
999.
S. J. Yeh C. S. Tsai H. T. Yang 《Journal of Radioanalytical and Nuclear Chemistry》1995,192(1):163-170
A preconcentration method of 13 rare earth elements (REES) was studied for neutron activation ananlysis (NAA). Hydrated magnesium oxide was used as the preconcentration agent to absorb the REES ions from aqueous solution onto the solid magnesium oxide, which was separated and analyzed. It was observed that the Langmuir equation for isothermal adsorption was well obeyed by the REES under the condition studied. The efficiency of the preconcentration process using hydrated magnesium oxide was critically examined for each of REE and for mixture of REES by preparing a known volume of solution containing known amount of trace REES. NAA was used to analyze REES recovered by the preconcentration process. It was found that the REES recoveries were satisfactory and the preconcentration process is reliable. There are several resort resort areas in Taiwan where local people are enjoying its hot spring water. It is generally believed that the hot spring water spa would bring about some sorts of therapeutic functions. The preconcentration method developed above, was applied to analyze the trace amounts of REES in hot spring wate in Taiwan. 相似文献
1000.
Identification and determination of geniposide contained in Gardenia jasminoides and in two preparations of mixed traditional Chinese medicines 总被引:7,自引:0,他引:7
A high-performance liquid chromatographic method was applied to the determination of the geniposide concentration in Gardenia fruit and preparations of traditional Chinese medicine using a mobile phase of acetonitrile-methanol-5 mM monosodium phosphate (pH 4.6) (5:15:80, v/v/v). Intra-assay and inter-assay accuracy and precision of the analyses were < or = 10% in the range of 0.1 through 50 microg/ml. The presence of geniposide in the medicinal herb and its preparations was ascertained by retention time, spiking with an authentic standard, change of detection wavelength and change of the composition of the mobile phase. The concentration of geniposide in the fruit of Gardenia jasminoides Ellis var. grandiflora Nakai is higher than that in Gardenia jasminoides Ellis. The concentration of geniposide in the traditional Chinese herbal medicine preparations, Huang-Lian-Jiee-Dwu-Tang (66.27 +/- 1.98 mg/g) and In-Chern-Hau-Tang (68.54 +/- 2.62 mg/g) was less than in the herb Gardenia jasminoides Ellis (73.44 +/- 2.62 mg/g) itself. 相似文献