Rate constants alkylamines

For reaction of Ph3CS0C6H4N02-/> with a series of ArNH2 in 45% dioxan / Nu is +1.5 (Ciuffarin et al., 1971). For the step in (176) with rate constant kt, / Nu is also large, +1.25 (Senatore et ah, 1971). However, reaction of a series of alkylamines, RNH2, with Ph3CSOC6H4N02-/> has a / Nu value of only +0.6 (Ciuffarin et al., 1971). Whether this large difference in / Nu actually means that the transition state is reached much earlier in terms of degree of... 

The proton transfer from multiply charged [cytochrome c] " (n = 7-9) to (/ )- and (5)-2-butylamine show a significant enantioselectivity." " Ions [cytochrome n = l-9) were produced by ESI and introduced into the analyzer cell of a FT-ICR containing an alkylamine, i.e., (/ )- and (5)-2-butyIamine, 1-propylamine, or tert-butylamine. Rate constants for the proton transfer are listed in Table 18. 

Table 18 Rate constants for the proton transfer from [cytochrome c] (n = 7-9) to alkylamines"...

In a subsequent investigation using the same phtalazine-derived ligand framework, urea substrates having alkyl substituents at only one of the N atoms, (e.g., A-methylurea or MW-dimethylurea) were shown to undergo alkylamine elimination to form a dinickel cyanate complex (120). The rate constants for the elimination of methylamine or dimethylamine at 60°C were calculated to be... 

The rate constant for aminolysis of a given 2-chloropyrimidine by an alkylamine is almost unaffected by increasing the chain length of by y-branching of the chain. A jS-branch has a small slowing influence, whereas one a-branch reduces the rate to 5%, and two a-branches reduce the rate to 0.1% of the corresponding /(-alkylamine (69M11). The reaction... 

Iron(n) (rf ).—Rate constants, and in some cases activation enthalpies and entropies, for the dissociation of a range of anions [Fe KCN)5L] have been reported. Ligands L include benzonitrile and the three dicyanobenzenes imidazole, glycine, and L-histidine and ammonia, alkylamines, and aniline, Fully reversible photoaquation has been demonstrated for the anion with L = benzonitrile. In many of these systems, rate constants for the reverse (formation) reaction, or for ligand replacement, have also been determined (see Chapters 7 and 8). 

The catalytic activity of alkylamines in the oxidation of anthrone by 2 in DMS decreased in the order primary > secondary > tertiary amines. The order of reaction for each of the reagents was determined, and the formation of complexes between anthrone and amines were confirmed and their formation constants and rate constant were determined. ... 

The kinetics of the reaction between D-glucose and several alkylamines have been examined by a potentiometric method, and the rate of formation of iV-glyco-sides [e.g. l-JV-(4-aminobenzoyl)-D-xylopyranosylamine] has been measured by determining the decrease of free amino-groups using l,2-naphthoquinone-4-sulphonic acid. Rate constants for the Maillard reaction of glycine with D-xylose, D-glucose, and D-fructose have also been reported. ... 

The aquation kinetics of the chloropentaamminecobalt(III) ion in water-ethanol mixtures has been studied. The rate constants correlate well with the Grunwald-Winstein Y parameter and with the dielectric constant of the medium. The data supports a D mechanism for the reaction. The loss of chloride from the complexes cw-[Co(en)2(NH2CH2CH20H)Cl] and cw-[Co(en)2(NH2(CH2)3 0H)Cl] has been studied in aqueous ethyleneglycol at 40-65 °C in acidic media and at 20-35 °C in basic media.The rate constants decreased linearly with the increasing mole fraction of the cosolvent. The loss of chloride resulted in the formation of the chelated amino-alcohols as the main product. The observed solvent isotope effect (A h2oAd2o) = 112 at 50 °C, [HCIO4] =0.01 moldm for chloride release is lower than the value reported for the aquation of the cw-[Co(en)2(alkylamine)Cl] complexes (1.38-1.44). This result may indicate the lack of direct solvent intervention in the act of substitution at the cobalt(III) center, as expected for a true intramolecular reaction. 

Table 1 Rate and equilibrium constants for 1 1 complexes of nickellji) with alkylamines...

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