Deuterio compound

Deuterio-3-iiitro-l,6-iiaphthyridiiie (168) was prepared from 4-chloro-3-iiitro-l,6-iiaphthyridiiie (166) by a reaction with tosyl hydrazide and subsequent hydrolysis of the 4-tosylhydrazino derivative (167) with Na2C03/ D2O solution (83RTC359). 7-Deuterio-l,8-naphthyridin-2(lH)-one was prepared by heating l,8-naphthyridin-2(lH)-one with deuterium oxide at 230°C for 35 h (85JHC761). Tliis deuterio compound could be converted into 2-chloro-(or 2-ethoxy-) 7-deuterio-3,6-dinitro-l,8-naphthyridine. 

Hixson<27) prepared the deuterio compound (31) and found that photolysis produced only compound (32) resulting from a di-n--methane rearrangement and not from a hydrogen migration ... 

If both a and [3-halogenosugars 8a and 8 c are reduced to the same anomeric mixture with the predominant deuterio compound 10, an easier cleavage of the axial anomeric carbon-bromine bond is observed with shorter times of photoreactions. 

Keyes, 1965 Norris and Osmundsen, 1965 Boulton and Clifford, 1965). The NMR spectrum of the potassium salt in dimethyl sulphoxide shows bands at — 8-93 and — 6-20 p.p.m. due to ring protons and an absorption at —6-55 p.p.m. (which disappears in the salt formed in D20) attributed to the added hydroxyl group. The latter two resonances are spin-spin coupled (J = 7 Hz). This spectrum does not by itself distinguish 49 from 50. However, Brown and Keyes experiments with the 5-deuterio compound have established that the addition occurs at C3, to give 49. The high reactivity of 4,6-dinitrobenzofuroxan is shown by the observation that the adduct is almost quantitatively formed in water without added hydroxide ions. 

The ratios of rate constants for the triple-proton transfer in protio- and deuterio-compounds [26] are determined to be A hhh/ hhd hhd/ hdd hdd/ ddd 3.6, and A hhh/ ddd 47 ( == 3.6 ) at 300 K, indicating that the logarithms of the rate constants change linearly upon deuteration of the N-H group (Aguilar-Parrilla et al., 1997). In the case where the triple-proton transfer occurs concertedly, the process can be interpreted by the two-site model (Fig. 15). In the transition state, three protons should be located in the middle between two adjacent nitrogen atoms. This interpretation is supported by ab initio calculations on the triple-proton transfer system (de Paz et al., 1997). 

Silane, germane, and stannane can be synthesized by the reduction of a variety of silicon, germanium, or tin compounds with active metal hydrides. The general method described below, involving the lithium hydroaluminate (LiAlHi) reduction of silicon tetrachloride and tin (IV) chloride, is convenient for the eflficient preparation of 1-50 mmoles of silane and stannane. The method is easily adapted to the synthesis of the deuterio compounds, i.e., silane-d4, germane-dt, and stannane-d4, by... 

One way we can explore the acidity of hydrogens with an organic molecule is to dissolve the compound in D2O in the presence of NaOD. If a hydrogen is removed by the base, it will be replaced by deuterium. For example, acetaldehyde, CH3CHO, in D20/Na0D is quickly converted to CD3CHO. What deuterio compounds would you get from each of the following compounds under those conditions ... 

Deuterio compounds. A mixture of 1,1,4,4-d4-buta-l,3-diene and trans- -cMoro-acrylic acid heated 80 hrs. at ca. 98° in a vacuum-sealed ampoule 3,3,6,6-d4-2-chlorohex-4-ene-l-carboxylic acid (Y ca. 70%) converted into the K-salt with aq. KHCOg, and warmed 4 hrs. at 50° with Nal in hexamethyl phosphoramide 3,3,6,6-d4-cyclohexa-l,4-diene. Overall Y 45%. W. P. Norris, J. Org. Chem. 33, 4540 (1968). 

Hexene converted to trihexylborane by treatment with borane in tetrahydro-furan, a soln. of diazoacetone in tetrahydrofuran added during ca. 20 min. with stirring and ice-cooling at 20°, stirred 0.5 hr. at room temp., then refluxed 0.5 hr. -> 2-nonanone. Y 65%. - As in other syntheses with organoboranes, only one of the alkyl groups of the intermediate trialkylborane is constructively consumed. F. e. s. J. Hooz and S. Linke, Am. Soc. 90, 5936 (1968) synthesis of diketones s. Chem. Commun. 1969, 139 synthesis of carboxylic acid esters and nitriles s. Am. Soc. 90, 6891 deuterio compounds s. Am. Soc. 91, 6195 (1969). 

A classic demonstration of this effect is in the racemization of the chiral biphenyl compound characterized by Mislow and shown in Eq. 8.6. Rotation about the central bond race-mizes the material and forces a severe steric clash between the two methyl groups in the transition state. Indeed, it is found that the deuterio compound racemizes faster than the protio, consistent with the notion that D is effectively smaller than H. The effect is certainly not a large one, as only a 15% difference is seen in a system with a really severe steric interaction and with multiple H/D substitutions. Nevertheless, steric isotope effects can be comparable to other secondary isotope effects, and so should be considered when evaluating experimental data. 

Deuterio compounds. -Ethyl-) -(3-thianaphthenyl) propionic acid heated on a steam bath with 10 parts Ni,Al-alloy and 10 parts Na-methoxide in deuterium oxide a-ethyl-y,d,d-trideuterio-y-phenylvaleric acid. Y 70-95%. F. e., also non-... 

Lithium tetradeuteridoaluminate Alcohols from carboxylic acid esters Deuterio compounds... 

Stereospecific dehydrogenation of deuterio compounds a,y -Ethyleneketones from ketones... 

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