Deuterated aniline

Larsson et al. 92) demonstrated also that the anisotropic pseudorotation model could be used for direct fitting of experimental PRE data for aniline protons in the complex between a Ni(II) chelate (Ni(II)(dpm)2) and ring-deuterated aniline in toluene-dg solution. The Ni(II) ion is in this case surrounded by four oxygen atoms and two nitrogen atoms, which should result in a sizable static ZFS, which indeed is confirmed by the fits. 

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. 

Kinetic studies of the aminolysis of bis(Y-phenyl) chlorophosphates ([YCgH40]2 (P=0)C1 Y = H, 4-Me, 4-MeO, 3-MeO) by anilines and deuterated anilines showed that the reaction proceeded via a stepwise mechanism, with rate-determining breakdown of the trigonal bipyramidal intermediate. The effects of solvents and solvent mixtures upon the rates of hydrolysis of diphenyl and bis-(2,4-dichlorophenyl) chlorophosphate showed that there were large sensitivities towards changes in solvent nucleophilicity, consistent with an 5 ivf2(P) process. ... 

Usually, molecular hydrogen does not play an important role in these catalytic reactions. This is also indicated by the fact that reducing PhN02 with Fe(CO)s catalyst, in the presence of a mixture of CO, D2O, and H2, the main product was deuterated aniline [17], although one should consider that H-D exchange on the product aniline may occur in solution. 

Aminolysis of methyl, " ethyl, propyl, " and isopropyl " phenylphosphonochlori-dothioates (RO)PhP(=S)Cl with substituted anilines XC5H4NH2 and deuterated anilines XC5H4ND2 at 333 K in MeCN yielded large inverse deuterium isotope effects of = 0.63-0.99 for the isopropyl ester consistent with backside attack in a concerted pathway and corresponding values of 1.02-1.48 for the methyl and propyl esters consistent with a predominant frontside attack, again in a concerted process. 

Preliminary NMR results on deuterated aniline in its Hofmann-type... 

Finally, Katritzky et al.sii have measured first-order rate coefficients for deuteration of pyrimidines by deuterated sulphuric acid (Table 152), and all pD and —D0 values given in the Table refer, as in the earlier work, to a temperature of 20 °C. For 2-aminopyrimidine, reaction clearly occurs on the free base and comparison of the data with the earlier work on anilines and by making a number of assumptions, conjugate acid at higher acidities is apparent and this follows the previously established pattern. This work yielded a value of 0.55 for [Pg.236]

The 13 C resonances in derivatives of aniline reveal that the carbon bearing a partially deuterated NH2 group appears as a multiplet because of the deuterium isotope effect on the 13C chemical shift, when the hydrogen exchange is low. This effect is larger for... 

In general, the literature contains fewer references to complexes formed from monofunctional amines than to those formed from ammonia itself or from multidentate amines. However, some clarification of earlier studies is to be found in recent reports, e.g. the complexes [Cd(PhNH2)X2] (X = C1 or Br), and their deuterated derivatives, have been reinvestigated and shown to be octahedral.166 This latter study clarified some of the confusion present in the earlier literature concerning these compounds. Another aniline complex, 3CdCl2-4L, has been studied and it has been shown that there are two types of octahedral environment in which the cadmium atoms are found, one comprising a CdCU unit and the other a CdCL unit.167... 

Anti-cancer drugs such as cyclophosphamide (15), aniline mustard, and nitrosoureas are transformed to reactive metabolites which are the toxic species required for their anti-cancer activity. Experiments with selectively deuterated analogs of these drugs has distinguished which pathway, among several alternative pathways of metabolism, is responsible for antitumor activity. For example, a deuterium isotope effect was observed for the formation of 4-ketocyclophosphamide (16), formed by the oxidation of the carbon alpha to the phosphoramide nitrogen, but there was no Isotope effect on the anti-tumor activity. However, there was a marked effect on the subsequent -elimination reaction and consequent decrease in anti-tumor activity by deuterium substitution at C-5. Thus, the formation of acrolein and phosphoramide mustard is rate determining for the anti-tumor activity of cyclophosphamide. 

Subsequent to the anthracene studies, picosecond-beam measurements of IVR in a number of other molecules have been made. These molecules include deuterated anthracenes,44 t-stilbene,45 and some alkyl anilines.46 One of the most significant results of these studies is that they have indicated that vibrational coherence30,40 (phase-shifted quantum beats) is a general phenomenon in molecules. Thus, it appears that an accurate understanding of IVR must rest firmly on an accurate understanding of vibrational coherence. 

Diazotisation of 15N-aniline followed by coupling of diazonium salt 216 with pyrazol-3-ones 215a,b gave 4-phenylhydrazono derivatives 217a,b. Through the use of 15N labeling and NMR spectroscopy it was shown that pyrazol-3-ones 217a,b exist entirely in the hydrazone form in deuterated chloroform. In hexadeuterated... 

Junk T, Catallo WJ, Civils LD (1997) Synthesis of polydeuterated benzothiazoles via supercritical deuteration of anilines. J Label Compd Radiopharm XXXlX(8) 625-630... 

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