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Isotopic labelling reactions

In conclusion, the tautomerization is intramolecular and the suprafacial 1,3 proton shift occurs across a azaallylic anion. The model differs slightly, however, from the biological system by providing competing stereochemical and isotope-labeling reactions pathways. Therefore, coenzymes carry out stereospecific reactions due to their apoenzymes, while nonenzymatic model reactions are not as stereospecific (310). [Pg.437]

Writing a ratio of reaction rates for two isotope labeled reactions we arrive at... [Pg.345]

The stereochemical relationship between the reactant and the product revealed by the isotopic labeling shows that oxygen becomes bonded to carbon on the same side from which H IS lost As you will see m this and the chapters to come determining the three dimensional aspects of a chemical or biochemical transformation can be a subtle yet powerful tool for increasing our understanding of how these reactions occur... [Pg.285]

When benzoic acid is allowed to stand in water enriched in isotopic label becomes incorporated into the benzoic acid The reaction is cat alyzed by acids Suggest an explanation for this observation... [Pg.813]

In an extension of the work described m the preceding section Bender showed that basic ester hydrolysis was not concerted and like acid hydrolysis took place by way of a tetrahedral intermediate The nature of the experiment was the same and the results were similar to those observed m the acid catalyzed reaction Ethyl benzoate enriched m 0 at the carbonyl oxygen was subjected to hydrolysis m base and samples were isolated before saponification was complete The recovered ethyl benzoate was found to have lost a por tion of Its isotopic label consistent with the formation of a tetrahedral intermediate... [Pg.855]

Alternatively, radiohalogen-labeled compounds may be prepared by way of isotopic labeling from the unlabeled bromo or iodo derivatives by various two-step reaction sequences. Examples include the use of trialkylsilyl synthons as described in References 10—13, and the use of boronic acid synthons as described in References 14 and 15. [Pg.480]

At least three distinct mechanisms can be written for these reactions. Write down some possible mechanisms, and suggest isotopic labeling studies that could distinguish among the possibilities you have proposed. [Pg.260]

The occurrence and extent of rearrangement of the 2-butyl cation have also been investigated by solvolysis studies using isotopic labeling. When 2-butyl tosylate is solvolyzed in acetic acid, C-2/C-3 rearrangement occurs only to the extent of 9% in the 2-butyl acetate which is isolated.Thus, under these conditions, most of the reaction proceeds by direct participation of the solvent. [Pg.320]

Other mechanisms must also operate, however, to account tor the fact that 5-10% of the product is formed with retained configuration at the chiral center. Isotopic labeling studies have also demonstrated that the 3-bromo-2-butyl radical undergoes reversible loss of bromine atom to give 2-butene at a rate which is competitive with that of the bromination reaction ... [Pg.711]

The most frequently encountered examples of cyclopropyl ring opening reactions in the steroid field are usually associated with angular or side chain methylation sequences. In fact, isotope labeling of the C-19 angular methyl group is the only reported application of this reaction for deuteration or tritiation pui poses. [Pg.206]

Isotope labeling by derivative formation with deuterated reagents is useful for the preparation of analogs such as dg-acetonides, da-acetates, da-methyl ethers, dg-methyl esters, etc. The required reagents are either commercially available or can be easily prepared. (The preparation of da-methyl iodide is described in section IX-F. Various procedures are reported in the literature for the preparation of dg-acetone, da-diazometh-ane57.i63.i73 and da-acetyl chloride. ) These reactions can be carried out under the usual conditions and they need no further discussion. A convenient procedure has been reported for the da-methylation of sterically hindered or hydrogen bonded phenolic hydroxyl functions by using da-methyl iodide and sodium hydroxide in dimethyl sulfoxide solution. This procedure should be equally applicable to the preparation of estradiol da-methyl ether derivatives. [Pg.211]

Evidence in support of the mechanism shown in figure 21.4 comes from isotope-labeling experiments. When 180-labeled methanol reacts with benzoic acid, the methyl benzoate produced is found to be l80-labeled but the water produced is uniabeled. Thus, it is the C-OH bond of the carboxylic acid that is broken during the reaction rather than the CO—H bond and the RO-H bond of the alcohol that is broken rather than the R-OH bond. [Pg.797]

One of the possibilities is to study experimentally the coupled system as a whole, at a time when all the reactions concerned are taking place. On the basis of the data obtained it is possible to solve the system of differential equations (1) simultaneously and to determine numerical values of all the parameters unknown (constants). This approach can be refined in that the equations for the stoichiometrically simple reactions can be specified in view of the presumed mechanism and the elementary steps so that one obtains a very complex set of different reaction paths with many unidentifiable intermediates. A number of procedures have been suggested to solve such complicated systems. Some of them start from the assumption of steady-state rates of the individual steps and they were worked out also for stoichiometrically not simple reactions [see, e.g. (8, 9, 5a)]. A concise treatment of the properties of the systems of consecutive processes has been written by Noyes (10). The simplification of the treatment of some complex systems can be achieved by using isotopically labeled compounds (8, 11, 12, 12a, 12b). Even very complicated systems which involve non-... [Pg.3]

The double isotope label technique and inorganic reaction mechanisms. J. O. Edwards and P. D. Fleischauer, Inorg. Chim. Acta, Rev., 1968, 2, 53-63 (35). [Pg.65]

Slightly removed from this in rigor is the use of a substituent to make a pure exchange into a net chemical reaction. No isotopic label is then needed. For example, the first reliable estimate of the rate constant for the exchange of ferrocenium ions and ferrocene was made on the basis of kinetic data for processes such as... [Pg.56]

Parallel and reversible reactions. The isomerization of allyl phenyl sulfide is a degenerate rearrangement made detectable by isotopic labeling of one end of the allyl group, permitting kinetic monitoring by NMR techniques.12... [Pg.65]

Much useful information has been obtained by using molecules that have been isotopically labeled and tracing the path of the reaction in that way. For example, in the reaction... [Pg.289]

For a review of the use of isotopic labeling to study Friedel-Crafts reactions, see Roberts, R.M. Gibson, T.L. Isot. Org. Chem., 1980, 5, 103. [Pg.749]


See other pages where Isotopic labelling reactions is mentioned: [Pg.230]    [Pg.734]    [Pg.112]    [Pg.539]    [Pg.84]    [Pg.230]    [Pg.734]    [Pg.112]    [Pg.539]    [Pg.84]    [Pg.826]    [Pg.852]    [Pg.228]    [Pg.475]    [Pg.193]    [Pg.634]    [Pg.824]    [Pg.225]    [Pg.225]    [Pg.315]    [Pg.630]    [Pg.826]    [Pg.852]    [Pg.38]    [Pg.311]    [Pg.284]    [Pg.22]    [Pg.7]    [Pg.8]    [Pg.350]    [Pg.433]    [Pg.55]   
See also in sourсe #XX -- [ Pg.87 , Pg.88 ]




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