Ammonium deuterated

Blackborow and Ridd51 studied the deuteration of aryl quaternary ammonium ions by deuterated sulphuric acid under second-order conditions (Table 173), and the results showed that, contrary to earlier beliefs, the positive nitrogen pole has... 

The occurrence of proton transfer reactions between Z)3+ ions and CHa, C2H, and NDZ, between methanium ions and NH, C2HG, CzD , and partially deuterated methanes, and between ammonium ions and ND has been demonstrated in irradiated mixtures of D2 and various reactants near 1 atm. pressure. The methanium ion-methane sequence proceeds without thermal activation between —78° and 25°C. The rate constants for the methanium ion-methane and ammonium ion-ammonia proton transfer reactions are 3.3 X 10 11 cc./molecule-sec. and 1.8 X 70 10 cc./molecule-sec., respectively, assuming equal neutralization rate constants for methanium and ammonium ions (7.6 X 10 4 cc./molecule-sec.). The methanium ion-methane and ammonium ion-ammonia sequences exhibit chain character. Ethanium ions do not undergo proton transfer with ethane. Propanium ions appear to dissociate even at total pressures near 1 atm. 

The application of deuterated ammonium formate as a deuterium source in transfer deuteration reactions of aromatic heterocycles has been reported by Derdau (Scheme 6.173 c) [329]. It was found that the reaction time could be reduced from 12-18 h (50 °C, oil bath) to 20 min at 80 °C by employing microwave irradiation, using deuteriomethanol as solvent and 10% palladium-on-charcoal as a catalyst. 

A rapid technique for the identification of surfactants in consumer products by ESI-MS was proposed by Ogura and co-workers [6], After a simple preparation procedure, infusion of the sample, which was prepared in a water/methanol mixture (50 50) containing 10 mM ammonium acetate, allowed assignment of the [M + NH4]+ ions of Cio- and Ci2-mono- and -diglucoside in the mass spectrum (ion masses as in Table 2.7.1). The approach even permitted quantitative analysis when deuterated internal standards were used. 

The determination of alkyltrimethyl ammonium compounds with the general formula RN (CH3)3X surfactant were performed using CF-FAB and ESI. The compounds examined were dodecyl-, tetradecyl-, and hexadecyl-trimethyl ammonium compounds dissolved in water. The product ion spectra of dodecyltrimethyl ammonium compound and its methyl-deuterated homologue were presented. The product ion at m/z 60 [(CH3)3NH]+of the non-deuterated compound at m/z 228 was the only ion that shifted after deuteration to m/z 69 [38],... 

Labelled [2H3]dodecyltrimethyl ammonium iodide ([2H3]Ci2TMAI) was synthesised as an internal standard for the quantitative determination of dodecyltrimethyl ammonium chloride (Ci2TMAC) in sewage and river water samples by using FAB-MS [117]. The synthesis of [2H3]Ci2TMAI involved the reaction of dimethylamino dodecane with deuterated methyl iodide (CD3I) in methanol. 

Mass spectra of ammonium nitrate and of a series of additional inorganic oxidizers were studied in both positive- and negative-ion mode by ESI-MS and ESI-MS/MS-CID [22, 23]. Characterization of ammonium nitrate by a series of typical cluster ions was confirmed by using isotojiicaUy labeled ammonium nitrate (ammonium- N, nitrate- N and nitrate- O) and deuterated water [22]. It was found that, at heated capiUary temperatures in the range... 

Another example of an achiral guest and a homochiral library was described in the work of Williams [9], which combined Co(II), bipy, and the homochiral ligand bipy. All possible combinations of A- and A-[Co(bipy ) (bipy)3 complexes were formed as confirmed by NMR and ES-MS. Treating with D-Cl was found to shift the speciation to only [Co(bipy)3] + and A-[Co(bipy )3] + (by NMR). Previous work on similar systems had shown that D-Cl deuterated the basic amine sites, and the resulting ammonium ions cooperatively bound two chloride ions [10]. In this example, addition of the achiral chloride ion amplified a single diastereomer of A-[Co(bipy )3] + (Fig. 5.9). 

When Tc is of the order of or less than spectral density of quanta is less. Thus, for example in a liquid, it is found that Ti decreases with increasing viscosity (increasing tc) to a certain point (tc Po) and then increases with increasing viscosity. A simple proportionality between Tc and the viscosity is given by the Debye theory of liquids. This dependence of Ti on has also been verified for several solids such as the ammonium halides (62), solid benzene, and partially deuterated benzenes (63). 

Shortly afterwards, this work was extended by the incorporation of a mass spectrometer into the system, thus enabling on-line NMR and MS data to be obtained with on-line collection of the eluent for off-line FT-IR spectroscopy [22]. The incorporation of the mass spectrometer required the addition of a small proportion of ammonium acetate, dissolved in methanol, to the deuterated chloroform used as the eluent in order to promote the ionisation of the analytes. The inclusion of methanol and ammonium acetate to the solvent obviously introduced new signals into the NMR spectra, and in addition resulted in the loss of exchangeable protons from the analytes which had been observable when chloroform alone was used as the solvent. This work demonstrated the feasibility of multiple hyphenation ( hypernation ) but the off-line nature of the FT-IR data acquisition, with the inevitable delay inherent in offline analysis, represents a slight disadvantage. In addition, volatile components may well be lost as the solvent is evaporated. This can be a problem that, together with analyte instability, is exacerbated with such interfaces when reversed-phase eluents are used since these require heating in order to ensure removal of the solvent. 

The infrared spectra of ammonium magnesium phosphate hexahydrate and its potassium analogue recorded at room temperature have already been studied [8] and the RT Raman spectrum of struvite has also been reported [9], In addition to that, our results of the study of the spectra of KMgP04-6H20 will be published shortly [10], To the best of our knowledge, the vibrational spectra of arsenstruvite and its deuterated analogues and also the vibrational spectra of the whole series of deuterated analogues of either of the three compounds have not been reported yet. 

Deuterated ammonium formate is found to reduce 4-carboxylpyridine iV-oxide in the presence of a palladium catalyst. Incorporation of a minimum of five deuteriums in the ring is achieved in good yield (Equation 99) <2004TL8889>. 

Hydrogen-bond configurations which combine the three-center bond with the bifurcated bond are observed in the crystal structures of violuric acid deuterate (Ihble 8.1) and the paraelectric ammonium sulfate as shown below... 

The lifetimes of hypervalent radicals have been found to depend rather dramatically on isotope substitution. For example, dimethyloxonium, (CH3)2OH, dissociates completely on a 1 -ps time scale when formed by collisional reduction of the stable cation (CH3)2OH+. By contrast, (CH3)2OD furnishes an abundant survivor ion in the +NR+ mass spectrum that is evidence that the deuterated hypervalent radical is metastable [178,179]. From the time scale of the NR measurements and the survivor ion relative intensities one can estimate that (CH3)2OH dissociates >5 times faster than (CH3)2OD. Similar isotope effects have been observed for CH3OH [180], C2H5OH [181], and hypervalent ammonium radicals, e.g., CH3NH [182], (CH3)2NH [60], (CH3)3NH [183], and [pyrrolidinium] [184], which are metastable only as deuterated species. 

Thus when molten ammonium trifluoroacetate (mp 130°C) is treated with LiH, deuteration studies show isotopic scrambling. Although it could be that D impinges only on the hydrogen of NHJ, another possibility is... 

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