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41.
Dan Haupt Curt Pettersson Douglas Westerlund 《Fresenius' Journal of Analytical Chemistry》1995,352(7-8):705-711
A three-factor central composite face design (CCF) has been used for the optimization of the chiral resolution of the enantiomers of alprenolol, oxprenolol, trimipramine and propranolol on CHIRAL-AGP. The variables (factors) investigated were pH and concentrations of the micellar agent Tween® 20 and heptanoic acid. The responses evaluated were resolution (RS), capacity factor (k) of the last eluted enantiomer and a chromatographic response function (CRF) defined as CRF = P5/log tret, where P is the peak-valley ratio according to Kaiser and tret is the retention time. The computed models, one for each substance and one for each response (in total 12 models), showed that the main factor for the regulation of RS as well as k and CRF in the experimental domain is the pH. The optimal pH for the substances could be found between pH 5.5 and 6.5. The optimum was evaluated by generating contour plots for the CRF models. The computed mathematical models were statistically evaluated and the predictive power of the models was tested by experimentation.Dedicated to Professor Dr. Dr. h.c. mult. J.F.K. Huber on the occasion of his 70th birthday 相似文献
42.
Photolysis of 3-pyridyldiazomethane in an Ar matrix at 7-10 K gives 3-pyridylcarbene. Further photolysis causes ring opening to nitrile ylide 26 (formonitrile pent-2-en-4-ynylide) as the major reaction together with a minor amount of ring expansion to 1-azacyclohepta-1,3,4,6-tetraene, 27. Matrix photolysis of 3-azidopyridine leads to ring opening to formonitrile N-cyanovinylmethylide, 33. 相似文献
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44.
Kathy E. Yokobata John M. Jordan Orvrlle Chapman Curt Krerl 《Photochemistry and photobiology》1986,43(4):391-401
Abstract— We have developed a procedure called a plaque reduction assay to assess the biological activity of duplex circular DNA modified by covalent adduct formation with psoralen derivatives. The replicating form (RF) of bacteriophage DNA modified by photochemical addition of a psoralen derivative was introduced into bacterial cells using the CaCI2 transfection method. The transfected cells. plated upon a confluent lawn of cells permissive for the bacteriophage in the inoculum, provided a measure of the reduction in infectivity of the RF DNA which resulted from its covalent modification. Use of this assay is illustrated in studies which screened and compared the activities of several recently synthesized psoralen derivatives. We describe two new compounds. β-(8-psoralenoxy)-ethanol and β-(8-psoralenoxy)ethylamine that are significantly more active than either 8-methoxypsoralen or trioxsalen in the biological assay 相似文献
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47.
Kvaskoff D Bednarek P George L Pankajakshan S Wentrup C 《The Journal of organic chemistry》2005,70(20):7947-7955
Flash vacuum thermolysis (FVT) of 9-azidophenanthrene 8, 6-(5-tetrazolyl)phenanthridine 18, and [1,2,3]triazolo[1,5-f]phenanthridine 19 yields 9-cyanofluorene 12 as the principal product and 4-cyanofluorene as a minor product. In all cases, when the product is condensed at or below 77 K, the seven-membered ring ketenimine 24 is detectable by IR spectroscopy (1932 cm(-1)) up to 200 K. Photolysis of Ar matrix isolated 8 at lambda = 308 or 313 nm generates at first the azirine 26, rapidly followed by the ylidic cumulene 27. The latter reverts to azirine 26 at lambda > 405 nm, and the azirine reverts to the ylidic cumulene at 313 nm. Nitrene 9 is observed by ESR spectroscopy following FVT of either azide 8, tetrazole 18, or triazole 19 with Ar matrix isolation of the products. Nitrene 9 and carbene 21 are observed by ESR spectroscopy in the Ar matrix photolyses of azide 8 and triazole 19, respectively. 相似文献
48.
Iminopropadienones, RN=C=C=C=O, can be generated from four different types of precursors in flash vacuum thermolysis reactions: 1,3-dioxane-4,6-diones 1, isoxazolopyrimidinones 2, pyridopyrimidinium olates 3, and pyridopyrimidinones 4. 2,6-Difluorophenyl-, 2,6-diethylphenyl-, o-tert-butylphenyl-, and mesityliminopropadienone have been directly observed by Ar matrix IR spectroscopy in one or more of these reactions. Reactions with bis-nucleophiles afford pyridopyrimidinones and perhydrodiazepinone derivatives. 相似文献
49.
Curt Wentrup 《Helvetica chimica acta》1972,55(2):565-569
Thermolysis of tetrazolopyrazine ( 1 ) in organic solvents gives pyrazinylnitrene ( 2 ) which undergoes ring contraction to 1-cyanoimidazole ( 3 ). 7-Methyl-5-methylthio-tetrazolo[1,5-c]pyrimidine ( 4 ) likewise gives 1-cyano-2-methylthio-4-methyl-imidazole ( 6 ). The two tetrazoles also undergo ring contraction to 1-cyanoimidazoles by gas chromatography, and 1 gives a low yield of 3 by photolysis. Thermolysis of 1 and 4 in cyclohexane gives aminopyrazine ( 7 ) and 6-amino-4-methyl-2-methylthio-pyrimidine ( 8 ), respectively. Tetrazolo[1,5-a]pyrimidines ( 9 ) give only 2-aminopyrimidines ( 10 ). 1-Cyanoimidazole, formed by thermolysis of 1 in acetic acid, reacts further to give 1-acetylimidazole, which with more acetic acid gives imidazole and acetic anhydride. An earlier report [2] of ring expansion of pyrazinylnitrene in acetic acid is discredited. In protic deuteriated solvents (D3O, CH3OD), tetrazolopyrazine reacts as an enamine, specifically exchanging H? C(6) for deuterium. 相似文献
50.
The concept of 1,3-dipolar cycloaddition was developed, starting in the late 1950s, largely by Rolf Huisgen and his students in Munich, and it has led to one of the most versatile methods for the construction of five-membered ring heterocycles. Although first known only as transient intermediates, nitrile imines have been at the heart of mechanistic studies of this type of cycloaddition reactions. Hundreds of mechanistic papers appeared in 1960s and 1970s; reliable spectroscopic observations were achieved in the early 1980s both at low temperatures and in the gas phase; finally, the first crystalline nitrile imine was reported in 1988. The unusual structures found by X-ray analyses as well as the facile rearrangements observed experimentally have fostered a new interplay between experiment and theory. The story of nitrile imines, from matrix characterization to stable compounds, nicely illustrates the role that main group elements can play in organic chemistry. 相似文献