Deuterium chloride

An extensive study of the A" -3-keto steroid system reveals a number of selective exchange reactions. For example, under controlled conditions in the presence of a strong acid catalyst such as deuterium chloride, it is... 

Instead of quenching with deuterium chloride, the intermediary organomonozinc compound can be used as a new nucleophile. Not only allylic halide but also alkenyl or aryl halide can be used as the first electrophile with bis(iodozincio)methane (3). In Scheme 23, examples for sequential coupling are summarized. In the case of coupling with bromoalkene, a nickel catalyst is more effective than a palladium catalyst. 

Schmidt, a complex is formed between methyl azide and antimony pentachloride in methylene chloride solution.1 1 Under the influence of dry hydrogen chloride, the complex decomposes at room temperature into methylenimmonium hexachloroantimonate (26) (Scheme V). By use of deuterium chloride instead of hydrogen chloride, N-monodeuterated methylenimmonium hexachloroantimonate was obtained. 

Deuterated C60 C60D36 was synthesized in n-hexane using the same procedure detailed above for C60H36 using Zn dust and 37% deuterium chloride (DC1) in heavy water (D20). After complete reduction also the electronic absorption spectrum of C60D36 is dominated by a maximum at 217 nm and the molar extinction coefficient was determined e217 = 16480 L cm-1 mol-1. 

C60 and C70 fullerenes were obtained from MTR and was 99.95% pure grade. n-Hexane (HPLC grade) tetradecane (special grade granted without olefins) and HC1 37% were obtained from Aldrich as well as the deuterium chloride (DC1) 37%... 

C70D38 was synthesized in n-hexane using the same procedure detailed above for C70H38 using Zn dust and 37% deuterium chloride (DC1) in heavy water (D20). 

Synthesis of Melphalan labelled at the nitrogen mustard function [40—42] or at the benzylic methylenic group [43] were reported. Deuteration at the positions ortho to the N-mustard substituent was reported when melphalan was refluxed in deuterium chloride in D2O (20% w/v) [44]. 

The compound is thermally unstable at room temperature and has an extrapolated boiling point of 27°. Boron exchange is observed with diborane(6) enriched in boron-10 109) and the SH proton exchanges with deuterium chloride 109>. The presence of the mercapto-group in the bridging position is unequivocally established by the boron-11 nmr... 

Fig. 4. The infrared spectrum of the dimethylether deuterium chloride complex in the gas phase. From J. E. Bertie and D. J. Millen, J. Chem. Soc. 514 (1965). Reproduced by permission from the Chemical Society...

Besides its use as a mechanistic probe, deuteriation of anions under kinetically controlled conditions is a potentially promising way to access deuteriated molecules in a regio- and stereo- controlled manner, in opposition to the thermodynamic equilibration in the presence of an excess of deuterium donor. Thus, treatment of the lithium anion of 2-methyltetralone (p E = 7.31, pfsfEa = 10.8, pKkr = 18.1 in water)335, by one equivalent of a solution of deuterium chloride in deuterium oxide, generates the intermediate O-deuteriated enol whose reaction with water or with an excess of deuterium chloride in deuterium oxide conducts to, respectively, the tetralone or the deuteriated tetralone (Scheme 69)336. 

Deuterium chloride was prepared by hydrolyzing acetyl chloride with excess deuterium oxide. The product was purified by fractional condensation in a high vacuum system and was stored in a borosilicate glass bulb attached to the vacuum manifold. 

The pathway by which the hydrogen chloride inhibits the telomerization and thus produces mono-ethylcyclohexane was supported by use of a solution of deuterium chloride (38%) in heavy water (99% deuterium oxide) as promoter under the standard conditions. The reaction mixture included 1.15 mols of cyclohexane and... 

Formation of ethylcyclohexane which is deuterated in the ring suggests that the cyclohexyl radical formed, for example as- in Equation 8, underwent intermediate exchange with the deuterium chloride. 

Calculations showed that the amount of deuterium in the cyclohexane, ethylcyclohexane and other hydrocarbons was actually more than that present in the deuterium chloride charged. Hence, it was concluded that the deuterium present in the deuterium oxide also underwent exchange. This was confirmed by analysis of the recovered acid solution. Its mass spectrum showed that most of the D2O was converted into DOH and H2O. Exchange of the proton of hydrogen chloride with deuterium of the "heavy water" occurred via formation of a hydrated proton, (H-OD2) in which the hydrogen and deuteriums are indistinguishable. 

CDCI3 = deuteriochloroform, DC1/D20 = 1 gm deuterium chloride in 10 gm deuterium oxide. 

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