Intrinsic gas-phase electrophilic reactivity of Ccclic N-alkyl- and N-acyliminium ions

he intrinsic gas-phase reactivity of cyclic N-alkyl- and N-acyliminium ions toward addition of allyltrimethylsilane (ATMS) has been compared using MS2 and MS3 pentaquadrupole mass spectrometric experiments. An order of electrophilic reactivity has been derived and found to agree with orders of overall reactivity in solution. The prototype five-membered ring N-alkyliminium ion 1a and its N-CH3 analogue 1b, as well as their six-membered ring analogues 1c and 1d, lack N-acyl activation and they are, accordingly, inert toward ATMS addition. The five- and six-membered ring N-acyliminium ions with N-COCH3 exocycclic groups, 3a and 3b, respectively, are also not very reactive. The N-acyliminium ions 2a and 2c, with s-trans locked endocyclic N-carbonyl groups, are the most reactive followed closely by 3c and 3d with exocyclic (and unlocked) N-CO2CH3 groups. The five-membered ring N-acyliminium ions are more reactive than their six-membered ring analogues, that is:  2a > 2c and 3c > 3d. In contrast with the high reactivity of 2a, its N-CH3 analogue 2b is inert toward ATMS addition. For the first time, the transient intermediates of a Mannich-type condensation reaction were isolatedthe β-silyl cations formed by ATMS addition to N-acyliminium ionsand their intrinsic gas-phase behavior toward dissociation and reaction with a nucleophile investigated. When collisionally activated, the β-silyl cations dissociate preferentially by Grob fragmentation, that is, by retro-addition. With pyridine, they react competitively and to variable extents by proton transfer and by trimethylsilylium ion abstractionthe final and key step postulated for α-amidoalkylation. Becke3LYP/6-311G(d,p) reaction energetics, charge densities on the electrophilic C-2 site, and AM1 LUMO energies have been used to rationalize the order of intrinsic gas-phase electrophilic reactivity of cyclic iminium and N-acyliminium ions.

Influence of the cutting edge micro-geometry of PCBN tools on the flank wear in orthogonal quenched and tempered turning M2 steel

Quenched and tempered high-speed steels obtained by powder metallurgy are commonly used in automotive components, such as valve seats of combustion engines. In order to machine these components, tools with high wear resistance and appropriate cutting edge geometry are required. This work aims to investigate the influence of the edge preparation of polycrystalline cubic boron nitride (PCBN) tools on the wear behavior in the orthogonal longitudinal turning of quenched and tempered M2 high-speed steels obtained by powder metallurgy. For this research, PCBN tools with high and low-CBN content have been used. Two different cutting edge geometries with a honed radius were tested: with a ground land (S shape) and without it (E shape). Also, the cutting speed was varied from 100 to 220 m/min. A rigid CNC lathe was used. The results showed that the high-CBN, E-shaped tool presented the longest life for a cutting speed of 100 m/min. High-CBN tools with a ground land and honed edge radius (S shaped) showed edge damage and lower values of the tool’s life. Low-CBN, S-shaped tools showed similar results, but with an inferior performance when compared with tools with high CBN content in both forms of edge preparation.