Spectroscopy and Absolute Reactivity of Ketenes in Acetonitrile Studied by Laser Flash Photolysis with Time-Resolved Infrared Detection

Abstract

Laser flash photolysis with time-resolved infrared detection of transients (LFP-TRIR) has been used to study the IR spectroscopy and reactivity of a number of substituted ketenes, prepared by the 308-nm photolysis of α-diazocarbonyl precursors in acetonitrile solution at room temperature. The correlation of the experimental ketene asymmetric stretching frequency to the Swain−Lupton field (F) and resonance (R) effect substituent parameters was unsatisfactory, whereas the correlation to the inductive substituent parameter (σI) of Charton gave excellent results. This suggests that the asymmetric stretching frequency of substituted ketenes depends mainly on the inductive (i.e., field) effect of the substituents. The mechanism and kinetics of the reactions of these ketenes with various amines in acetonitrile were also studied. An intermediate species identified as either zwitterionic ylide or amide enol formed in the nucleophilic addition of the secondary amine to the Cα of the ketene is observed by TRIR. The decay of this species is assisted by the amine and is concomitant with the formation of an amide, the final product of the reaction. Our kinetic data on ketene amine reactions show a general trend, indicating a much higher reactivity (ca. 3 orders of magnitude difference in the corresponding rate constants) of secondary amines compared with that of tertiary amines. Secondary diethylamine shows reactivity similar to those observed for primary amines, while secondary piperidine seems to be, in general, somewhat more reactive. The observed trend is rationalized in terms of the steric effects exerted by both amine and ketene substituents. Our data on para-substituted phenyl ketenes provide support for the negative charge development on the ketene moiety in the transition state, with electron-withdrawing substituents accelerating and electron-releasing substituents slowing down the addition reaction.

Determination of Mechanism for Soot Oxidation with NO on Potassium Supported Mg‐Al Hydrotalcite Mixed Oxides

“…2, after heating at 500°C for 20 min, a band at 2162 cm -1 arises (see Fig. 2b), which can be attributed to the ketene group [25,26]. This band reaches maximum after 100 min (see Fig.…”

In Situ FT-IR Spectroscopic Studies of CO Adsorption on Fresh Mo2C/Al2O3Catalyst

“…A protective and amorphous surface oxide slightly greater than one monolayer thick is produced. 42 As shown in Figure 2 and 24 and CCO species 45,46 could be possible assignments for this band. However, this band cannot be attributed to CO adsorbed on Mo 5+ or just Al 3+ sites because adsorbed CO on these two sites can be easily removed by evacuation at room temperature.…”

Tautomerism of lactones and related compounds. Mass spectrometric data and theoretical calculations

“…12 In addition, for carboxylic acids, the very low relative stability of their enols is a well known fact, 4,13 although some of these short-life tautomers were prepared as intermediate compounds. [14][15][16][17][18][19][20] There are few studies about lactone tautomerism. This family of compounds exhibits great biological interest.…”