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91.
Quarternary phosphonium and ammonium salts attached to polystyrene resins by short (2 - 3 atom) carbon chains are highly active phase transfer catalysts for a variety of nucleophilic substitution reactions. 相似文献
92.
N. Omenetto S. Nikdel R.D. Reeves J.B. Bradshaw J.N. Bower J.D. Winefordner 《Spectrochimica Acta Part B: Atomic Spectroscopy》1980,35(8):507-517
Relative ionic and atomic fluorescence profiles for barium have been obtained in an argon inductively coupled plasma by exciting different transitions with a nitrogen-laser pumped tunable dye laser and measuring the resulting fluorescence pulses with a boxcar averager. Spatially resolved profiles are directly obtained without the need of an Abel inversion procedure, with a volume resolution of approximately 0.2 mm3. The profiles are given along the excitation axis as well as along the observation axis, for different heights above the coil and different input powers. At low heights, the ion profile resembles a hollow pencil with a typical double-peaked, asymmetric distribution, while the atom profile seems to be complementary to the ion profile. Some scatter from water is also evident at low heights. 相似文献
93.
The molecule N,N-dimethylacetoacetamide, which is subject to a keto–enol equilibrium process in solution, also exhibits hindered rotation about the amido N? C bond. The hindered rotation rates have been studied by lineshape fit methods of the nuclear magnetic resonance spectra. In spite of some overlap of the keto and enol N-methyl proton signals, the simultaneous measurement of the two distinct energy barriers in the two forms is possible as well as a determination of the keto–enol equilibrium. The differences in free energy of activation between keto and enol forms for the rotation barrier can be related to the conjugation energy of the N? C π system with the enolic hydrogen bonded ring. Appeal to the model compound acetylacetone reveals a consistent set of energies for the keto and enol forms in the ground and transition states for internal rotation. The opportunity has been taken to reexamine and compare the keto–enol system ethylacetoacetate. Long range, solvent, concentration and temperature sensitive scalar couplings 4J(HH) between the enolic –OH and the adjacent methyl group in acetoacetic ester have not hitherto been reported. 相似文献
94.
In the presence of NaBH(OAc)(3), a 1,5-keto-aldehyde, contained within a side-chain of an eta(4)-dienetricarbonyliron complex, undergoes a double reductive amination sequence with a series of primary amines, to provide the corresponding piperidine products in good to excellent yield. The dienetricarbonyliron complex functions as a powerful chiral auxiliary in this cascade process, exerting complete control over the stereoselectivity of the reaction, with the formation of a single diastereoisomeric product. The sense of stereoinduction has been confirmed by X-ray crystallography. Removal of the tricarbonyliron moiety can be effected with CuCl(2) to afford the corresponding 2-dienyl-substituted piperidine in excellent yield. Attempted extension of this cyclisation strategy to the corresponding azepane ring system using a 1,6-keto-aldehyde as the cyclisation precursor was unsuccessful; in this case, the reaction stopped after a single reductive amination on the aldehyde to provide an acyclic keto-amine product. 相似文献
95.
Nakamura S Wada M Crabtree BL Reeves PM Montgomery JH Byrd HJ Harada S Kuroda N Nakashima K 《Analytical and bioanalytical chemistry》2007,387(6):1983-1990
A sensitive semi-micro column HPLC method with peroxyoxalate chemiluminescence (POCL) detection and column switching has been
developed for simultaneous determination of 3,4-methylenedioxymethamphetamine (MDMA) and related compounds, for example 3,4-methylenedioxyamphetamine,
methamphetamine, and amphetamine, in hair. After digestion of the hair with 1 mol L−1 sodium hydroxide the compounds were extracted with n-heptane and derivatized with 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole. A mixture of hydrogen peroxide and bis(2,4,5-trichloro-6-carbopentoxyphenyl)oxalate
in acetonitrile was used as post-column CL reagent. Calibration plots showed linearity was good (r = 0.999); detection limits were 0.02–0.16 ng mg−1 hair at a signal-to-noise ratio of 3. The precision of the method, as RSD (n = 5), in intra-day and inter-day assays was better than 5.0 and 6.9%, respectively. The proposed method was sufficiently
sensitive to detect low ng mg−1 levels of MDMA and related compounds in hair, and could be used for quantification of the compounds in hair samples from
patients treated in a chemical dependency unit. 相似文献
96.
How quickly can a listener focus on a single tonal cue that indicates the frequency of an upcoming signal? Initial measurements were made with frequency uncertainty (signal frequency varies randomly from trial to trial) and with certainty (same frequency on all trials). Measured by a yes-no procedure, thresholds for 40- and 20-ms signals presented in continuous broadband noise at 50 dB SPL were higher in uncertainty than in certainty; the difference decreased monotonically from 5 dB at frequencies below 500 Hz to under 3 dB above about 2500 Hz. This decrease in the detrimental effect from uncertainty, which comes about with increasing signal frequency, may result from preferential attention to higher frequencies. In a second experiment, frequency again varied randomly, but each trial now began with a cue at the signal frequency. The critical variable was the delay from cue onset to signal onset. A delay of 352 ms eliminated the detrimental effect of frequency uncertainty at all frequencies. At the shortest delays of 52 and 82 ms the detrimental effect was reduced primarily at lower frequencies. Our analysis suggests that shifting focus to a cued frequency region, under optimal stimulus conditions, requires less than 52 ms. 相似文献
97.
Reeves DC Rodriguez S Lee H Haddad N Krishnamurthy D Senanayake CH 《Organic letters》2011,13(9):2495-2497
The palladium catalyzed alkoxycarbonylation and aminocarbonylation of vinyl tosylates are described. A variety of ketone and aldehyde derived vinyl tosylates may be carbonylated in the presence of primary, secondary, and tertiary alcohols, or primary and secondary amines, to provide the corresponding esters and amides in good yields. The alkoxycarbonylation was applied to a short synthesis of isoguvacine. 相似文献
98.
99.
W. Preston Reeves Cuong V. Lu Brian Schulmeier Lynette Jonas Oyvind Hatlevik 《合成通讯》2013,43(3):499-505
In aqueous polar solvents, various aromatic ethers were selectively brominated using pyridinium hydrobromide perbromide. 相似文献
100.