Metal tritiates

When specifically labelled compounds are required, direct chemical synthesis may be necessary. The standard techniques of preparative chemistry are used, suitably modified for small-scale work with radioactive materials. The starting material is tritium gas which can be obtained at greater than 98% isotopic abundance. Tritiated water can be made either by catalytic oxidation over palladium or by reduction of a metal oxide ... 

However, in olefin polymerization by two-component catalysts during polymerization not only active transition metal-polymer bonds are formed, but also inactive aluminum-polymer ones, as a result of the transfer process with the participation of a co-catalyst (11, 162-164). The aluminum-polymer bonds are quenched by tritiated alcohol according to the scheme (25), so an additional tagging of the polymer occurs. The use of iodine (165, 166) as a quenching agent also results in decomposing inactive metal-polymer bonds. 

Olefin polymerization by catalysts based on transition metal halogenides is usually designated as coordinated anionic, after Natta (194). It is believed that the active metal-carbon bond in Ziegler-Natta catalysts is polarized following the type M+ - C. The polarization of the active metal-carbon bond should influence the route of its decomposition by some compounds ( polar-type inhibitors), e.g. by alcohols. When studying polymerization by Ziegler-Natta catalysts tritiated alcohols were used in many works to determine the number of metal-polymer bonds. However, as it was noted above (see Section IV), in two-component systems the polarization of the active bond cannot be judged by the results of the treatment of the system by alcohol, as the radioactivity of the polymer thus obtained results mainly from the decomposition of the aluminum-polymer bonds. 

The tritiated version could be prepared from tritiated formic acid which we had prepared at high specific activity (2.5 Ci mmol-1) by a metal-catalyzed hydrogen-tritium exchange procedure using T2 gas. The material can be stored either as a solid or as a solution if the latter any release of tritium by back exchange can be easily monitored by 3H NMR spectroscopy. In our experience very little exchange occurs over several weeks of storage [51]. 

As of now no details of the synthesis of optically active tritiated compounds produced under microwave-enhanced conditions have been published. Another area of considerable interest would be the study of solvent effects on the hydrogenation of aromatic compounds using noble-metal catalysts as considerable data on the thermal reactions is available [52]. Comparison between the microwave and thermal results could then provide useful information on the role of the solvent, not readily available by other means. 

Another synthetic route which gives a good yield of the labelled tin hydride involves the hydrolysis of an organometallic intermediate such as a trialkylstannyllithium46 with deuterated or tritiated water. The trialkylstannyllithium can be prepared by treating the trialkyltin chloride with lithium metal in THF46. This process is shown in equation 42. 

Group VIII transition metal catalyzed hydrogen exchange reactions are important in providing useful information concerning the fundamental processes of bond rupture and bond formation on catalyst surfaces. The reactions are also a convenient source of deuterated and tritiated compounds for chemical and biological research (i). 

The most direct route towards functionalized aliphatic polyesters is based on the functionalization of polyester chains. This approach is a very appealing because a wide range of functionalized aliphatic polyesters could then be made available from a single precursor. This approach was implemented by Vert and coworkers using a two-step process. Eirst, PCL was metallated by lithium diisopropylamide with formation of a poly(enolate). Second, the poly(enolate) was reacted with an electrophile such as naphthoyl chloride [101], benzylchloroformate [101] acetophenone [101], benzaldehyde [101], carbon dioxide [102] tritiated water [103], ot-bromoacetoxy-co-methoxy-poly(ethylene oxide) [104], or iodine [105] (Fig. 26). The implementation of this strategy is, however, difficult because of a severe competition between chain metallation and chain degradation. Moreover, the content of functionalization is quite low (<30%), even under optimized conditions. 

By Reduction of Unsaturated Precursors The method of choice for labeling with tritium is the reduction of a suitable unsaturated precursor (containing a double bond, carbonyl group, etc.) with carrier-free tritium gas or tritiated metal hydrides. The major limitation of this method is the availability of a suitable unsaturated precursor of the desired compound. It is essential to carry out the synthesis in a non-hydroxylic solvent (dioxane, ethyl acetate, etc.). Reductions carried out in alcohol or water will lead to almost complete exchange of the tritium gas with the solvent. 

Similarly, when, attempted tritiation of the anthryllithium 30 with T20 as an external quench failed because of competing protonation, the solution was to use T20 as an internal quench halogen-metal exchange of 29 proceeds in the presence of the T20 at -70 °C.36... 

By contrast with the radiation-induced procedures, isotope exchange reactions catalyzed by Group VIII transition metals are applicable to both deuterium and tritium labeling of heterocyclic compounds. Because of recent mechanistic developments in this field, it is possible to predict with some degree of certainty the reactivity of a molecule for deuteration and also for moderate levels of tritiation. If compensation for additional radiation-induced interactions is made, then the theory also satisfactorily explains high specific activity tritiations. 

Heterogeneous metal catalysis is the most useful general method for the deuteration and/or tritiation of heterocyclic compounds.57 It involves exchange between the organic substrate and isotopic hydrogen (as water, usually, or gas) in the presence of a Group VIII transition metal catalyst at temperatures up to 180° [Eq. (18)]. 

Tritiated quencher, e.g., ROT Number of metal-polymer bonds (MPB)... 

D and E being atoms or groups of atoms easily detected in the polymer). BD and E (also called quenchers) are typically a hydroxy-tritiated alcohol and 35S02, respectively. The common feature of these methods is that the quenchers react not only with the growing chain, but also with non-propagative metal-polymer... 

It has many applications as a tracer, for example, to study the movement of ground waters, and to study the al sorption of hydrogen by metals and the absorption of hydrogen on metal surfaces. Many deuterated and tritiated compounds have been synthesized and studied. Some of the important physical properties of the isotopes of hydrogen are listed in Table 8-2. 

When using, however, two-component catalysts alcohols also react with inactive metal-polymer (aluminium-polymer) bonds which are formed in the chain transfer reactions with a cocatalyst. It is expedient to use the alcohol method only for catalytic systems and polymerization conditions for which the number of inactive metal-polymer bonds is low. Such a case is the polymerization of 4-methyl-1-pentene on vanadium trichloride activated with various organoaluminium compounds. For this system the influence of catalyst composition and polymerization conditions on Cp and kp was determined by quenching the polymerization with tritiated alcohol. 

Significant contamination of desiccants (silica gel, zeolite and CaS04) was observed in unsealed containers exposed to tritiated concrete powder at room temperature and in a refrigerator. This contamination was not seen for metals and plastics. 

The termination reactions appear to be quantitative and specific for the reaction of saturated polymer molecules attached to aluminium and titanium [116], but applied to diene polymerizations the method is less satisfactory mainly because of the greater stability of allylic carbon-transition metal bonds. Polybutadiene has been labelled by terminating with tritiated methanol with the Cr(acac)3/AlEt3 catalyst [55], and similarly polyisoprene prepared with VCl3/AlEt3 [107]. Polybutadiene prepared with Til4/Al(i-Bu)3 has been labelled using C02 [115]. 

The proportion of catalyst consumed at conversions in the region of 2.6—4.8% ranged from 0.008 to 0.012 using C labelled catalyst, while the fraction of growing chains determined by quenching with tritiated water ranged from 0.001—0.002. Most of the chains attached to transition metal were inactive and the estimated fraction of prope ating chains was 1/4300. Values for the rate coefficients are (units, mole, 1, sec). 

Site-specific tritium-labeled arenes. Taylor reports that tritium-labeled aromatics can be obtained by wetting dried ether with tritiated water, adding an aryl halide, cooling to -70°, and then adding n-butyllithium. Trimethylsilyl derivatives of aromatics can be prepared using trimethylchlorosilane in the same way. When the organometaUic intermediate is formed first and then treated with tritiated water, only the unlabeled hydrocarbon is obtained in some cases. Apparently, the cross-metalation reaction is faster than the reaction of -butyl-lithium with either water or trimethylchlorosilane. 

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