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111.
2-Methyl- and 2,4-dimethylbenzophenone were irradiated with the unsymetrical dienophiles methyl acrylate, acrylonitrile, methyl methacrylate and methyl propiolate. The dienols additions proceed regiospecifically yielding in each instance a single hydroxylic compound having the car?ylate or the carbonitrile group in vicinal position. Syntheses of 1,2,3,4-tetrahydro- and 1,4-dihydronaphthols with various substituents were thus achieved. 3,4-Dihydronaphthalenes and naphthalenes were also obtained by dehydration. 2,4-dimethylbenzophenone was irradiated with acetylenedicarbonitrile yielding the dehydrated addition product 6-methyl 1-phenylnaphthalene-2,3-dicarbonitrile. 相似文献
112.
Clark SB O'Rangers JJ Rowe WD Madson MR Hurlbut JA Sofos JN Fuerst B James G Griffith S Readnour RS 《Journal of AOAC International》2002,85(6):1260-1267
The objective of this study was to compare 2 methods for the determination of tilmicosin residues in bovine liver samples. Three laboratories participated in the comparison of the 2 methods. The first method was described in a New Animal Drug Application (NADA 140-929), and the second was a modification of that method in which hexane was substituted for carbon tetrachloride in one cleanup step. Each of the 3 laboratories analyzed subsamples of 10 bovine livers containing incurred tilmicosin. Residues ranged from 2.3 to 81 ppm tilmicosin in the 10 liver samples with an 11.8% relative standard deviation obtained by using both methods. In addition, fortified-control liver tissue samples were analyzed concurrently with tissues containing incurred residues by using the modified method in one of the laboratories. The fortification levels ranged from 0.3 to 112 ppm, with recoveries ranging from 76 to 92%. The results from the 3 laboratories were comparable, indicating that the modified method was not only as effective as the original NADA method, but also more desirable because of the change to a less hazardous solvent. 相似文献
113.
Johnson JE Dolliver DD Yu L Canseco DC McAllister MA Rowe JE 《The Journal of organic chemistry》2004,69(8):2741-2749
Kinetics and stereochemical studies have been carried out on the reactions of the Z and E isomers of O-methylbenzohydroximoyl halides [1Z and 1E, ArC(X)=NOCH(3)] with sodium methoxide in 9:1 DMSO-methanol. The reactions of methoxide ion with hydroximoyl fluorides (X = F) are stereospecific. The reaction with 1Z (X = F) gives only the Z substitution product (1Z, X =OCH(3)). The reaction of methoxide ion with 1E (X = F) is less selective, giving ca. 85% E substitution product. The Hammett rho-values for the Z and E isomers (X = F) are +2.94 and +3.30, respectively. The element effects for 1Z (Ar = C(6)H(5)) are 2.21 (X = Br):1.00 (X = Cl):79.7 (X = F). The 1E element effects are (Ar = C(6)H(5)) 1.00 (X = Cl):18.3 (X = F) and (Ar = 4-CH(3)OC(6)H(4)) 1.97 (X = Br):1.00 (X = Cl):12.1 (X = F). The entropies of activation for these reactions are negative (for example, DeltaS() = -15 eu for 1Z and DeltaS() = -14 eu for 1E, Ar = 4-CH(3)OC(6)H(4), X = F). These experimental observations are consistent with a mechanism proceeding through a tetrahedral intermediate. Ab initio calculations were carried out to help explain the stereospecificity of these reactions. These calculations indicate that the tetrahedral intermediate from the Z isomer undergoes rapid elimination to the Z substitution product before stereomutation can take place. These calculations also show that the lowest barrier for rotation around the carbon-nitrogen single bond in the tetrahedral intermediate derived from 1E leads to an intermediate that eliminates fluoride ion to give E product. 相似文献
114.
Derivatives of Meldrum's acid and the sodium salts of substituted malonic esters undergo rapid arylation in high yield when treated with aryllead triacetates. These reactions have been applied to the synthesis of ibuprofen, an analgesic, and in a closely related reaction 5-ethylbarbituric acid has been reacted with phenyllead triacetate to give phenobarbital. 相似文献
115.
Thirty elements are determined in coal and fly ash by instrumental neutron-activation analysis using both thermal and epithermal irradiation. Gamma-ray spectra were recorded 7 and 20 days after the irradiations. The procedure is applicable to the routine analysis of coals and fly ash. Epithermal irradiation was found preferable for the determination of Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, Cs, Ba, Sm, Tb, Hf, Ta, W, Th and U, whereas thermal irradiation was best for Sc, Cr, Fe, Co, La, Ce, Nd, Eu, Yb and Lu. Results for SRM 1632 (coal) and SRM 1633 (fly ash) agree with those of other investigators. 相似文献
116.
Engineering a polyketide with a longer chain by insertion of an extra module into the erythromycin-producing polyketide synthase 总被引:4,自引:0,他引:4
Rowe CJ Böhm IU Thomas IP Wilkinson B Rudd BA Foster G Blackaby AP Sidebottom PJ Roddis Y Buss AD Staunton J Leadlay PF 《Chemistry & biology》2001,8(5):475-485
BACKGROUND: Modular polyketide synthases catalyse the biosynthesis of medically useful natural products by stepwise chain assembly, with each module of enzyme activities catalysing a separate cycle of polyketide chain extension. Domain swapping between polyketide synthases leads to hybrid multienzymes that yield novel polyketides in a more or less predictable way. No experiments have so far been reported which attempt to enlarge a polyketide synthase by interpolating additional modules. RESULTS: We describe here the construction of tetraketide synthases in which an entire extension module from the rapamycin-producing polyketide synthase is covalently spliced between the first two extension modules of the erythromycin-producing polyketide synthase (DEBS). The extended polyketide synthases thus formed are found to catalyse the synthesis of specific tetraketide products containing an appropriate extra ketide unit. Co-expression in Saccharopolyspora erythraea of the extended DEBS multienzyme with multienzymes DEBS 2 and DEBS 3 leads to the formation, as expected, of novel octaketide macrolactones. In each case the predicted products are accompanied by significant amounts of unextended products, corresponding to those of the unaltered DEBS PKS. We refer to this newly observed phenomenon as 'skipping'. CONCLUSIONS: The strategy exemplified here shows far-reaching possibilities for combinatorial engineering of polyketide natural products, as well as revealing the ability of modular polyketide synthases to 'skip' extension modules. The results also provide additional insight into the three-dimensional arrangement of modules within these giant synthases. 相似文献
117.
118.
119.
Steven?D?Buckingham Luanda?Pym Andrew?K?Jones Laurence?Brown Mark?SP?Sansom David?B?Sattelle Philip?C?BigginEmail author 《BMC neuroscience》2005,6(1):2
Background
Nicotinic acetylcholine receptors (nAChRs) are pentameric proteins that are important drug targets for a variety of diseases including Alzheimer's, schizophrenia and various forms of epilepsy. One of the most intensively studied nAChR subunits in recent years has been α7. This subunit can form functional homomeric pentamers (α7)5, which can make interpretation of physiological and structural data much simpler. The growing amount of structural, pharmacological and physiological data for these receptors indicates the need for a dedicated and accurate database to provide a means to access this information in a coherent manner. 相似文献120.
Proposals have been made to utilise arrays of GaAs lasers in optical computer memories. For fast, random access to data the use of acousto-optical deflectors seems feasible. The number of lasers for use with each deflector is normally severely limited, because of the bandwidth limitation which is inherent in acousto-optic devices. This note describes a technique whereby the bandwidth limitation can be largely overcome, so that light from many lasers can be deflected by a single deflector. 相似文献