Deuterium chloride, preparation

In deuterium-labeling experiments, 4,4-diphenylcyclohexanone (2) reacted with zinc dust/deuterium chloride (prepared from trimethylchlorosilane and deuterium oxide), and gave 4,4-dideuterio-l,l-diphen-ylcyclohexane (3) as the major product (isotopic purity of 81% d2, 10% d, 6% ds and 3% cU equation 7)," while the ketone (4) was converted to (5) in 83% isotopic purity, along with the trideuterio compound (17%), under rather vigorous conditions (equation 8). ... 

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 required deuterium chloride is prepared either outside the reaction medium by the action of deuterium oxide on phosphorus trichloride or thionyl chloride or by hydrolysis of an acid chloride in the reaction vessel. Shiner14 gives an example of the latter method in the preparation of 1,1-dimethyl [2-D] isobutyl chloride ... 

When deuterated compounds were being first prepared, the reduction of aliphatic halogen compounds to the corresponding deuterium compounds was effected mainly by potassium or aluminum amalgam in D20 the preparation of acetic acid from potassium trichloroacetate53 and of methane from bromoform54 may be cited as examples. Later, reduction by zinc in an acid medium was preferred 4d 5 5 for instance, thymine was labelled in the methyl group by reduction of (chloromethyl)uracil with zinc and deuterium chloride 24... 

The synthesis of deuterium chloride (CP ) requires the preparation of completely deuterated sulfuric acid. This material is prepared from sulfur trioxide and 99 % deuterium... 

The two analytical problems associated with the preparation of deuterium chloride (CP ) are analysis of the product for CP content and for deuterium content. The radio-... 

At 0 °C, a 2.0 M solution of n-butyllithium (0.11 mol) in pentanes (or the same amount of ethereal methyllithium) is added to phenylacetylene (11 mL, 10 g, 0.10 mol) in diethyl ether (10 mL). A 1.5 M ethereal solution of deuterium chloride,freshly prepared and stored in a Schlenk buret at -25 °C, follows immediately afterward. The solvent is removed by slow distillation through a 20 cm long Widmer column. Short-path distillation of the remainder gives a colorless liquid (93% bp 141-143 °C 1.5523). The infrared... 

Wells and coworkers53 have prepared a series of deuterated tetramethyltin compounds, which they used to study the long-range deuterium isotope effects on the proton chemical shifts of tetramethyltin. The various deuterated tetramethyltin compounds, with one to four trideuteromethyl groups on the tin atom, were prepared by a series of methyl group exchanges beginning with tri-trideuteromethyltin chloride and undeuterated tetramethyltin (Scheme 12). 

The reaction between deuterium and 1-butyne, 2-butyne, 1,2-butadiene, and 1,3-butadiene, respectively, was conducted in a flow system at near ambient temperatures. The catalyst (0.03 wt % palladium on alumina) was prepared by impregnating hard alumina pellets with palladium chloride so that the metal was probably confined to an outer shell of each particle. 

Acyl complex XVI was prepared from 3-perdeuteriophenyl-3,3-dideu-teriopropionyl chloride (XV), and its rate of decarbonylation (Reaction 9) along with that of the undeuteriated complex was measured at 80 °C. The rate constants (KH = 3.34 X 10 5, Kv = 4.75 X 10"6) show a primary deuterium isotope effect of 7.04. These results are also consistent with... 

Bis(phenylselanyl)methyllithiums 429 (R = H) are stable till 0 °C and were initially trapped with deuterium oxide, methyl iodide and benzophenone639. a-Substituted organolithium intermediate 429 (R = Me, w-CgH ), prepared with LiTMP in THF/HMPA at — 20 °C, reacted with alkyl bromides, ethylene oxide and benzaldehyde to give products 430 in good yields (Scheme 113)640. Bis(methylselanyl)methyllithiums 431 have been allowed to react with different electrophiles to afford products 432 (Scheme 113)640. Alkylated products have been deprotected with mercury(II) chloride or copper(II) chloride/copper(II) oxide, and by oxidation with hydrogen peroxide or benzeneseleninic anhydride644. Deprotection of selenoacetals to ketones can also be performed with sulfuric acid645. 

Recently methyltriphenylammonium tetrafluoroborate was prepared from triphenylamine and trimethyloxonium fluoroborate. Demethylation was affected by butyllithium in hexane or methylene chloride and with phenyllithium in benzene or ether. No evidence for biphenyl or diphenyl-methylamine was noted and only triphenylamine was characterized. In demethylation reactions with potassium methoxide in methanol-O-d, no exchange of methyl hydrogen for deuterium was observed. Thus, no proton abstraction processes occurred in these decompositions 114>. 

The mechanism of the oxidation of primary amines to nitriles with cuprous chloride-dioxygen-pyridine mixtures has recently been investigated by measuring the hydrogen-deuterium kinetic isotope effect in the oxidation of benzylamine to benzonitrile. In earlier work , the authors reported that nitriles could be prepared from amines in almost quantitative yield and high purity using this cuprous chloride reagent. 

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