Sodium deuteroxide

To obtain a good yield and high isotopic purity, it is more important to carry out the preparation and purification of the Raney nickel as fast as possible (in 30 min or less) than to wash the nickel free of sodium deuteroxide. 

Table 2. Dehydrofluorination of erythro- and threo-a-Bromo-a -fluorosucdtiic Acids by Sodium Deuteroxide in Deuterium Oxide [35]...

In a dry 250-ml. Erlenmeyer flask equipped with a Teflon-coated magnetic stirring bar is placed 11 ml. of a solution (Note 5) containing 0.01 mole of sodium deuteroxide in 10 ml. of deuterium oxide and 1 ml. of anhydrous tetrahydrofuran. 

After the solution has been cooled in an ice bath, 120 ml. of the ethereal solution containing 0.039 mole of diazomethane is added, the flask is stoppered loosely with a cork, and the reaction mixture is stirred vigorously at 0° for one hour. The lower deuterium oxide layer is removed with a pipette and a fresh 11-ml. portion of the sodium deuteroxide solution is added. This mixture is then stirred for one hour at 0°, and the process is repeated until a total of four exchanges have been performed. The ethereal diazomethane solution is then decanted into a clean, dry 250-ml. Erlenmeyer flask and dried over 10 g. of anhydrous sodium carbonate. The resulting solution (approximately 110 ml.) contains (spectrophotometric analysis, Note 4, or titration with benzoic acid, Note 3) 0.020-0.022 mole (51-56%) of dideuteriodiazomethane which is 98-99% deuter-ated (Note 6). 

Dehydration of hetisine diacetate (126) with phosphorus oxychloride and pyridine followed by basic hydrolysis afforded a mixture of olefins 136 and 137, whose structures were analyzed by H-NMR spectroscopy. These olefins can only be derived from hetisine diacetate if its structure is 126, a fact requiring the structure of hetisinone to be 128. Furthermore, hetisinone is stable to bases, behavior that is consistent with the assigned structure but less likely for either of the alternative /J-ketoalcohols 134 and 135. When hetisinone was heated in D2O-CFI3OD containing sodium deuteroxide, a mixture of deuterated hetisinones was obtained. Mass spectral analysis revealed the presence of 14% d, 53% d2, 24% d3, and 6% dA species. These data further confirmed that hetisinone is correctly represented as 128. 

Oxidation of O-methyldeacetyllythramine (75) with chromic anhydride-pyridine complex yielded the ketone (79) which exchanged four hydrogens on treatment with sodium deuteroxide in deuterium oxide and deutero-methanol (12). 

Using this method, 4-phenylquinazoline (66% mp 95-97°C) can be prepared from 4-phenyl-2-[7V -(/)-toluenesulfonylhydrazino)]quinazoline. By decomposition of deuterated A-[N - p-toluene,sulfonylhydrazino)]quinazoline hydrochloride with sodium deuteroxide in deuterium oxide, [4- H]quinazoline can be obtained (21% mp45°C). ... 

Dipole moments of 3-aminopyrazine 1-oxide (3.43D, dioxane) (749) and 3,5-bisdimethylaminopyrazine 1-oxide (4.87, benzene) (663) have been measured. Second-order rate constants for hydrogen-deuterium exchange of H2 and in sodium deuteroxide-deuterium oxide solutions of 3-amino- and 3-dimethylaminopyrazine 1-oxides have been determined as 2.3 x 10 , 1.1 x 10 , and 3.3 x 10 and 4.5 x 10 l/mol min, respectively. These results (and those of other 3-substituted pyrazine 1-oxides) have been correlated with o constants, and the log of the H2 exchange rates has been shown to be linearly related to the p/fa values of these compounds (745). 

A more direct approach is to use sodium deuteroxide in deuterium oxide to remove the aluminum from the Raney alloy. The activity of the resulting catalyst depends on the temperature and duration of the leaching process. Washing the catalyst with deuterium oxide and/or dioxane gives an effective catalyst for deuteration reactions. 

Treatment of ent/o-tricyclo[3.2.1.0 ]octane with mercury(II) acetate as electrophile gave endo-4-(acetoxymercurio)-e tfo-2-methoxybicyclo[3.2.1]octane (18a) as the sole product, which was reduced with sodium amalgam in sodium deuteroxide to the corresponding 4-deuterio derivative 18b.83,84 Using the e co-isomer as the substrate gave a 1 1 mixture of exo-[4- HJ-exo-2-methoxybicyclo[3.2.1]octane (19b) and 5yn-7- [ H,]-methyl -ex o-2-methoxybicyclo[2.2.1]hep-tane (20b) after reduction. ... 

IH- and 13C-NMR solution spectra were determined on a Jeol FX90Q spectrometer. The sample ( 20 mg) was added to 0.5 cm of deuterium oxide. A few drops of 1 mol dm 3 sodium deuteroxide were added until the sample dissolved. 

There is another application for electrophilic substitution in SCW. The use of supercritical D2O presents the opportunity of producing deuterated organic compounds, e.g. complete deuterated aniline (78 % yield of completely deuterated product, 400 °C, 12 h reaction time [53]) in the presence of sodium deuteroxide. 

The formulation of compounds 169 and 171 as 3H- and not IH-derivatives is supported by their PMR spectra. In CDCI3, compound 171 shows a one-proton singlet at 8 6.59 which is not deuterium exchangeable in sodium deuteroxide-deuterium oxide. This signal is assigned to the benzylic proton in the 3-position. The tetrahydro analogue 169 (Ar = Ph) shows a similar signal at 5 5.54. The ultraviolet spectra of compounds 169 and 171 have also been discussed. In methanol the dihydro derivative 171... 

Benzylpenicillin is rapidly converted to (5R,6R)-benzylpenicilloic acid (8) when dissolved in D2O containing sodium deuteroxide as seen by absence of the closely-placed 5-H, 6-H doublets (5.4, 5.46 ppm, separation 4 Hz) characteristic of an intact ) -lactam ring, while the progressive conversion of the... 

Phenol in 10% sodium deuteroxide in deuterium oxide upon treatment with Raney nickel-aluminium alloy and heating at100 C for 3 hours afforded a pentedeurated product in 86% yield (ref.63). 

Baldwin and Widdison prepared ethyl a-deuterodiazoacetate by reacting ethyl-diazoacetate with two different batches of sodium deuteroxide in deuterium oxide containing hexadecyltrimethylammonium bromide as a phase transfer catalyst. A proton NMR analysis showed the product was more than 98% deuterated at the a-carbon. The deuter-ated diazoacetate was then converted into two diastereomeric ethyl-(2-bromo-2-methylcyclopropane-1 -d) carboxylates by reaction with 2-bromopropene and a rhodium(II)... 

Terminal alkynes with > 99% deuterium at the terminal position can also be obtained after several treatments with excess sodium deuteroxide in D2O (equation 101). 

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