Radioactivity benzene

The radioactive isotopes available for use as precursors for radioactive tracer manufacturing include barium [ C]-carbonate [1882-53-7], tritium gas, p2p] phosphoric acid or pP]-phosphoric acid [15364-02-0], p S]-sulfuric acid [13770-01 -9], and sodium [ I]-iodide [24359-64-6]. It is from these chemical forms that the corresponding radioactive tracer chemicals are synthesized. [ C]-Carbon dioxide, [ C]-benzene, and [ C]-methyl iodide require vacuum-line handling in weU-ventilated fume hoods. Tritium gas, pH]-methyl iodide, sodium borotritide, and [ I]-iodine, which are the most difficult forms of these isotopes to contain, must be handled in specialized closed systems. Sodium p S]-sulfate and sodium [ I]-iodide must be handled similarly in closed systems to avoid the Uberation of volatile p S]-sulfur oxides and [ I]-iodine. Adequate shielding must be provided when handling P P]-phosphoric acid to minimize exposure to external radiation. 

Evidence for this mechanism is that optically active PhCHDCHs labeled in the ring with C and treated with GaBr3 in the presence of benzene gave ethylbenzene containing no deuterium and two deuteriums and that the rate of loss of radioactivity was about equal to the rate of loss of optical activity." The mechanism of intramolecular rearrangement is not very clear. The 1,2 shifts of this kind have been proposed " ... 

Like Halpem, Siekierska and Siuda with GeCl in benzene, Riedel and Merz found essentially the same distribution of radioactivity following p decay of Ge04 as by nuclear reactions, except for a uniformly higher yield of As 03. They analyse their results for this reaction as 14% failure of bond rupture, 5% radical recombination and, in benzene solution, 4% additional reaction with radiation produced radicals. 

Radioactivity Analysis. Samples of urine, feces, and tissues were combusted to COo and analyzed for radioactivity (5). By using this method the recovery of radioactivity from samples spiked with C was 95 dt 5%. To determine the radioactivity expired as CO2, 5-ml aliquots of the solution used to trap the CO2 were added to 15 ml of a scintillation counting solution containing 4 grams 2,5-diphenyloxazole (PPO) and 0.1 grams l,4-bis-2(5-phenyloxazolyl)-benzene (POPOP) per liter of 1 1 toluene 2-methoxyethanol. Samples were counted for radioactivity in a Nuclear Chicago Mark II liquid scintillation counter. Counting eflSciency was corrected by the internal standard technique. 

Dibenzenechromium was studied by Baumgartner et al. 15). They found that the yield of Cr(Ph)2 was 11.8%. [One cannot fail to be struck by the similarity in yields of FeCp2, RuCp2, and Cr(PhH)2, although it may well be merely coincidence.] On heating the irradiated samples to 110°C, they found the yield to increase to 19.4%. It was found that dissolution of the radioactive crystals in benzene yielded no further Cr(PhH)2. This stands in contrast to the above-mentioned results of Zahn and Harbottle which, though not strictly comparable, show Cp to be quite reactive toward ruthenium atoms. Dibenzenechromium was also formed in low yield 14) from neutron irradiation of PhHCr(CO)3, as will be discussed in more detail later. 

It is quite possible that more highly dehydrogented products (e.g. hexadiene or hexatriene) may also be involved in the reaction sequence. However, none of these species was observed in the GLC. This is not surprising since both these species are highly reactive and may not have accumulated to any measurable extent. One could have used labeled diolefins or triolefins in mixture with n-hexane to test this possibility. Although this experiment was not attempted, we would speculate that most of the radioactivity would have been quickly incorporated into the benzene with a small amount perhaps flowing temporarily upstream into the olefins and the paraffin. 

Even though cyclohexane is rapidly converted into benzene under these conditions, the results in Figure 3 clearly prove that it cannot be a gas phase intermediate in the n-hexane reaction. If it were, there would have been radioactivity in the unreacted cyclohexane when it was mixed with labeled n-hexane none was observed. This proves that the cyclization step must be further along the reaction stream and must not involve an olefin forming cyclohexane which then dehydrogenates to the aromatics. 

When a sample of phenylalanine carrying a 14C label in the benzene ring was photolysed at 254 nm, it gave radioactive 2-allylglycine (2-aminopent-4-enoic acid, 16). This showed that the irradiation had disrupted the aromatic ring [23],... 

The three components involved in the mixtures all give benzene. A fraction of benzene should be radioactive, and its specific activity will reflect how much of this product was formed from the radioactive and how much from the inactive component of the starting mixture. 

The components of the starting mixture are in rapid adsorption-desorption interaction with the surface. For example, a part of adsorbed -hexane desorbs as -hexane another part reacts to give benzene. If benzene formation involves an n-hexene surface intermediate, this hexene—the concentration of which may be eventually so small that it does not appear in the gas phase—interacts with the inactive hexene in the starting material and increases its specific radioactivity. 

Recent work (Brown and Pearsall, 15) has indicated that while hydrogen aluminum tetrachloride is nonexistent, interaction of aluminum chloride and hydrogen chloride does occur in the presence of substances (such as benzene and presumably, olefins) to which basic properties may be ascribed. It may be concluded that while hydrogen aluminum tetrachloride is an unstable acid, its esters are fairly stable. Further evidence in support of the hypothesis that metal halides cause the ionization of alkyl halides (the products of the addition of the hydrogen halide promoters to the olefins) is found in the fact that exchange of radioactive chlorine atoms for ordinary chlorine atoms occurs when ferf-butyl chloride is treated with aluminum chloride containing radioactive chlorine atoms the hydrogen chloride which is evolved is radioactive (Fair-brother, 16). 

It has been pointed out that the product obtained by treating certain samples of ground a-titanium trichloride (particularly those which contain traces of TiCU or other Ti(IV) compounds) with radioactive alkylalu-minum, shows a certain degree of radioactivity also after submitting it to the action of an acid or an alcohol in an attempt to decompose the metal-carbon bonds. Such radioactivity is due to a contaminant, the nature of which depends on the degree of purity and the amount of crude a-titanium trichloride employed. It generally decreases, eventually attaining very low values if the crude a-titanium trichloride is repeatedly washed with anhydrous benzene before its use. 

Filtering and washing of the solid phase at a given temperature, under nitrogen, with carefully purified anhydrous benzene (or other hydrocarbon solvent) until any radioactivity disappears from the washing solvent. 

In 1904, long before the advent of radioactive tracers, Knoop synthesized fatty acids labeled by chemical attachment of a benzene ring at the end opposite the carboxyl group. He prepared these compounds with both odd and even numbers of carbon atoms in straight chains and fed them to dogs. From the dogs urine he isolated hippuric acid and phenylaceturic acid, which are the amides of glycine with benzoic acid and phenylacetic acid, respectively. Knoop showed that the phenylacetic acid was produced from those fatty acids with an... 

The capture process of the electron capture detector can be very temperature-sensitive. The sensitivity may either increase or decrease with an increase in temperature, depending on the compound involved, as illustrated in Figure 6.24 for three benzene derivatives. Since detector temperature may affect sensitivity it is sometimes possible to improve the analysis by operating at a different temperature. The radioactive source determines the maximum temperature limit for the detector which is listed in Table 6.6. Exact values vary with manufacturer. 

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