Deutero methanol

HsC6—CO—C6H5 ———3/24 stdn. Diphenyl-deutero-methanol-O-D 67%d. Th. 

D20 is even more polar than D4-methanol and rather limited in its use for that reason - usually for salts only. Like deutero methanol, it exchanges all acidic protons readily and exhibits a strong HOD signal at about 4.9 ppm. Samples made up in D20 often fail to dissolve cleanly and benefit from filtration through a tight cotton wool filter (cf. Section 2.4.1). 

Halcinonide dissolved in either methanol, deutero-methanol, aqueous ammonia-methanol, or deuterium oxide deuter-ated ammonia-methanol solvents appears stable after storage for six days at 50°, using nuclear magnetic resonance and mass spectrometry.70... 

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). 

Hydrazine Methanol Fluoroethylene Deutero compounds Oxygen... 

Of course, you don t have to use either of the above standards at all. In the case of samples run in deutero chloroform/methanol and dimethyl sulfoxide, it is perfectly acceptable, and arguably preferable, to reference your spectra to the residual solvent signal (e.g., CD2HOH) which is unavoidable and always present in your spectrum (see Table 2.2). These signals are perfectly solid in terms of their shifts (in pure solvent systems) though the same cannot be said for the residual HOD signal in D2O and for this reason, we would advise adhering to TSP for all samples run in D20. 

The mass spectrum of compound 1 and of its 3-deutero derivative has been reported.33 Apart from a strong molecular ion, the principal feature is a peak at 91 m.u. due to a C6H5N radical ion. This ion or interconverting ions 139-141, which are obtained from many other compounds, heterocyclic and nonheterocyclic, have been studied by the technique of collision-induced decomposition (CID).210 A study of some triazolopyridine-7-methanols has shown that other pathways, notably loss of the CHN2 fragment, can become important.23... 

In 1975, we discovered that photolysis of aryldisilanes produces a novel type of the silicon-carbon double-bonded intermediate (83). The structure of this intermediate is quite different from that of the diphenylsilaeth-ene reported by Sommer et al. A transient formation of the reactive intermediate can be confirmed by trapping experiments. Thus, the photolysis of p-tolylpentamethyldisilane with a low-pressure mercury lamp in the presence of methanol- affords 1,4- and 1,6-adducts, 1-methoxydimeth-ylsilyl-4-methyl-5-deutero-6-trimethylsilyl-1,3-cyclohexadiene, and 1-methoxydimethylsilyl-3-deutero-4-methyl-6-trimethylsilyl-l,4-cyclohexa-diene in 27 and 28% yield (Scheme 11). In this photolysis, monodeutero methoxydimethylsilyltoluene to be expected from the reaction of the sila-ethene intermediate, p-CHsC6H4Si(Me)=CH2, with methanol- produces in only 2% yield (84). 

It is difficult to choose a reference compound against which to judge the stability of the dication. That it can be formed at all, however, is suggestive of special stabilization associated with the two TT-electron system. The dianion formed by adding two electrons to the TT system of cyclobutadiene also meets the 4 - -2 criterion. In this case, however, four of the six electrons would occupy HMO nonbonding orbitals, so high reactivity could be expected. There is some evidence that this species may have a finite existence. " Reaction of 3,4-dichlorocyclobutene with sodium naphthalenide, followed a few minutes later by methanol-0-<7 gives a low yield of 3,4-di-deutero-cyclobutene. The inference is that the dianion [ 4114 ] is present, but there has not yet been direct experimental observation of this species. Cyclooctatetraene is reduced by alkali metals to a dianion. 

Isomerization of l-deutero-l,3-dimethylindine at 30°C in pyridine,benzene, and methanol, using DABCO as catalyst, occurs with relative rates of 6.5, 1.14, and 1.0 respectively24 . The low relative rate in methanol is probably due to hydrogen bonding between the solvent and catalyst. The relative rates in the two aprotic solvents decrease in order of the decreasing dielectric constants of the solvents. 

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