Toluene deuteriated

Analogous investigations of deuteriated methanol were carried out on the OD-valency vibration roD = 2689 cm in CCI4 as the standard solvent (Tamres, 1952, Searless and Tamres, 1951). Altogether 12 aromatic compounds, including halogen-substituted ones, were used as solvents. In the series of solvents, carbon tetrachloride, benzene, toluene, 0-, m-, j-xylene and mesitylene, i/qd shifted from 2689 to 2670 in benzene and to 2655 cm in mesitylene. 

The interesting explanation offered by Wexler for this discrepancy is based on a striking parallel with the behaviour of the isomeric deuteriated toluenes under electron impact. The mass spectrometric work by Meyerson and Rylander (1957), Rylander et al. (1957) and by Meyerson et al. (1968), provided convincing evidence that the isomeric tolyl and benzyl ions produced by electron impact rearrange, before fragmentation, to a common seven-membered ring structure, the tropylium ion, which... 

A number of other diazocompounds have been studied. Warren (1961) has shown that the reaction of 9-diazofluorene in ethanol and in ethanol-water mixtmes is similar to that of diphenyldiazomethane. The rate of reaction is slower in deuteriated solvent and the operation of general acid catalysis was inferred from measurements with picric acid. As would be expected from the conjugation between the diazo and dibenzo-cyclopentadienyl groups in 13, the rate of reaction is slower than that of DDM (by a factor of about twelve) and there seems little doubt that both substrates react with a rate-determining proton transfer. Bate studies with substituted diazofluorenes yield a value of — p = l 6-l-9 depending on the substituent constants used (Warren, 1963 Warren and Yandle, 1965). This value is similar to that for the reaction of substituted diphenyldiazomethanes in toluene and is a further indication that the stability of diazoalkanes is quite sensitive to substituent effects. 

With acetic anhydride, the nitrone (23) was unchanged, but with toluene-p-sulphonyl chloride in heterogeneous alkaline medium (23) gave the oxaziridine (30), whereas in a neutral solvent it led to (31) (Scheme 4). Conditions for deuteriation of the nitrone (23) were established in heterogeneous neutral medium, no deuteriation occurred in homogeneous alkaline medium, quantitative deuteriation at C-21 was effected in heterogeneous alkaline medium, deuteriation was incomplete, but in heterogeneous acidic medium, rapid incorporation was observed. ... 

The CAD MIKE spectra of [ArS02] ions deriving from methyl-deuteriated 127d and from unlabelled p-toluene-iV-butylsulfonamide (103d) displayed the same decomposition pattern and the expected mass shifts83, pointing to the same structure, or mixture of structures. 

The benzyl radical and several deuteriated isotopomers have been generated in methylcyclohexane at 4.2 K by UV-photolysis of toluene or deuteriated toluene, and a detailed vibrational analysis of the fluorescence spectra carried out. The photodissociation dynamics of azulene at 193 nm have been studied in a molecular beam using multimass ion-imaging techniques. Most of the excited molecules produced at this wavelength relax rapidly to the electronic ground state through internal conversion, then isomerize to naphthalene, and eventually dissociate by H-atom elimination. 

The R—H bond rupture followed by the formation of the metal-alkyl bond Pt—R is the rate-determining step in the activation of saturated hydrocarbons by metal complexes. The exchange rate decreases with the increase of branching in the hydrocarbon molecules. The scheme in equation 188 illustrates the simultaneous formation of organic chlorides and unsaturated hydrocarbons besides the deuteriation of saturated hydrocarbons (methane, ethane, propane, n-butane, i-butane, n-hexane, c-hexane, toluene in 0.1-0.7M water solutions of H2PtCl6, containing 5%K2PtCl4 at 120 °C in sealed ampoules . ... 

Conformational studies of block copolymers have also been very rewarding. The system PS-PMMA diblock copolymer has been studied, by deuteriating the styrene segment, and using SANS and light scattering techniques in toluene. The radii of gyration of PSD homopolymer (M = 88 000) measured by both methods and that of PMMA block (M = 203 000) in the diblock copolymer... 

Radicals in Solutions of 1,3,5-Trinitrotoluene and Toluene and their Deuteriated Analogues at 200 K", J. Phvs. Chem.. in press. 

The advances in understanding of the chemistry of norbornyl cations (discussed in a later section) have become less dramatic. In an interesting series of papers, Stille and his colleagues have reported results of importance to an understanding of the stereoselectivity of the corresponding anions. Suitable hydrazines and toluene-p-sulphonyl hydrazides were prepared and decomposed in deuteriated solvents either by oxidative cleavage or by basic cleavage. Study... 

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