Deuterium labelling with

The title compound has been deuterium labelled with H at C(3) (1), and in the vinyl group (2) by deuterium exchange of the enolizable hydrogen atoms in 3 followed by... 

The first mass spectrometric investigation of the thiazole ring was done by Clarke et al. (271). Shortly after, Cooks et al., in a study devoted to bicydic aromatic systems, demonstrated the influence of the benzo ring in benzothiazole (272). Since this time, many studies have been devoted to the influence of various types of substitution upon fragmentation schemes and rearrangements, in the case of alkylthiazoles by Buttery (273) arylthiazoles by Aune et al. (276), Rix et al. (277), Khnulnitskii et al. (278) functional derivatives by Salmona el al. (279) and Entenmann (280) and thiazoles isotopically labeled with deuterium and C by Bojesen et al. (113). More recently, Witzhum et al. have detected the presence of simple derivatives of thiazole in food aromas by mass spectrometry (281). 

Sometimes the strongly basic properties of Gngnard reagents can be turned to synthetic advantage A chemist needed samples of butane specifically labeled with deuterium the mass 2 isotope of hydrogen as shown... 

Radiolabeled folate provides a powerful tool for folate bioavaHabiUty studies in animals and for diagnostic procedures in humans. Deuteration at the 3- and 5-positions of the central benzene ring of foHc acid (31) was accompHshed by catalytic debromination (47,48) or acid-cataly2ed exchange reaction (49). Alternatively, deuterium-labeled fohc acid (32) was prepared by condensing pteroic acid with commercially available labeled glutamic acid (50). 

Intermolecular reactions with typical cycloaddition components are also possible. Phenyl isocyanate in ether converts triisopropyldiaziridinimine (182) to the 1,2,4-triazolidine under mild conditions. Labeling with a deuterated isopropyl group revealed that cycloaddition is not preceded by N—N cleavage, which should have resulted in deuterium randomization (77AG(E)109). 

In neutron reflectivity, neutrons strike the surface of a specimen at small angles and the percentage of neutrons reflected at the corresponding angle are measured. The an jular dependence of the reflectivity is related to the variation in concentration of a labeled component as a function of distance from the surface. Typically the component of interest is labeled with deuterium to provide mass contrast against hydrogen. Use of polarized neutrons permits the determination of the variation in the magnetic moment as a function of depth. In all cases the optical transform of the concentration profiles is obtained experimentally. 

Nucleophilic substitution in cyclohexyl systems is quite slow and is often accompanied by extensive elimination. The stereochemistry of substitution has been determined with the use of a deuterium-labeled substrate (entry 6). In the example shown, the substitution process occurs with complete inversion of configuration. By NMR amdysis, it can be determined that there is about 15% of rearrangement by hydride shift accon any-ing solvolysis in acetic acid. This increases to 35% in formic acid and 75% in trifiuoroacetic acid. The extent of rearrangement increases with decreasing solvent... 

The occurrence of syn elimination in 5-decyl systems has been demonstrated with the use of diastereomeric deuterium-labeled substrates. Stereospecifically labeled 5-substituted decane derivatives were prepared and subjected to appropriate elimination conditions. By comparison of the amount of deuterium in the E and Z isomers of the product, it was... 

The di-7r-methane rearrangement has been studied in a sufficient number of cases to develop some of the patterns regarding substituent effects. When the central sf carbon is unsubstituted, the di-7i-methane mechanism becomes less favorable. The case of 1,1,5,5-tetraphenyl-l,4-pentadiene is illustrative. Although one of the products has the expected structure for a product of the di-7t-methane rearrangement, labeling with deuterium proves that an alternative mechanism operates ... 

A deuterium labeling study has been performed with the results shown. Discuss the details of the mechanism that are revealed by these results. Is there a feasible mechanism that would have led to B having an alternative label distribution ... 

The reduction of oxime derivatives (section IV-C) is useful for the preparation of steroidal amines labeled with a deuterium on the nitrogen-bearing carbon atom... 

Deuterioboration of 5a-cholest-2-ene (171), followed by oxidation of the alkylborane intermediate with hydrogen peroxide in the presence of sodium hydroxide, illustrates the application of this method for the preparation of c/5-deuterium labeled alcohols.(For the preparation of tra 5 -deuterium labeled alcohols see section VII-A.) The predominant reaction product is 2a-di-5a-cholestan-3a-ol (172, 1.03 D/mole) which is accompanied by 3a-di-5a-cholestan-2a-ol (173) and other minor products." ... 

Only one of these methods, namely the reaction of halides with lithium aluminum deuteride, is a true displacement reaction, following the same course as the previously discussed displacement of sulfonate esters (section Vl-A). Thus, lithium aluminum deuteride treatment of 7a- and 7jS-bromo-3 -benzoyloxy-5a-cholestanes (195) and (196) gives the corresponding deuterium labeled cholestanols (197) and (198) respectively." ... 

Treatment of oc-cyclopropyl ketones with lithium in a mixture of N,N-d2 propylamine and hexamethylphosphortriamide is a recently reported method for deuterium labeling via reductive ring opening. This reaction provides y-labeled ketones in good yield (70-100%) and isotopic purity (85-93%). 

Deuterium labeling of C-18 has also been accomplished by an alternate procedure adapted from the Nagata steroid synthesis. During the course of the total synthesis of pregnanolone, thevC-18 function is introduced in the form of a nitrile group. Reduction of this function in intermediate (247) with lithium aluminum deuteride leads to a deuterated imine (248), which upon Wolff-Kishner reduction and acid-catalyzed hydrolysis... 

During the course of a mass spectrometric study of D-homo-14-hydroxy steroids, it was necessary to prepare the corresponding C-8 deuterium labeled analogs. The preparation of these uncommon steroid derivatives has been achieved by repeating the Torgov total synthesis [(257) (262)] with a deuterium-labeled bicyclic starting material (258). Both of the resulting 14-hydroxy epimers, (261) and (262), exhibited better than 90% isotopic purity. ... 

During an attempt to metalate a glycal with /-BuLi, it was discovered by deuterium labeling that a TBDMS ether can be deprotonated. °- ... 

Denitration of nitro compounds with Bu- SnD provides an elegant method fci the synthesis of deiuerated compounds Recently, the synthesis of deuterium labeled plant sterols has been reported fsee Eq 11%)... 

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