Thermodynamic properties of S-(−)-nicotine

Alkaloids and Selected Topics in Their Thermochemistry

“…There are disappointingly few contemporary determinations of the enthalpy of formation of any alkaloid. These new measurements of alkaloid enthalpies of formation include those of berberine chloride dihydrate (21) (often, but erroneously, named the hydrochloride salt) [8] and nicotine (22) [9]. These species have the following systematic names: 5,6-dihydro-9,10-dimethoxy-benzo[g]-1,3-benzodioxolo [5,6-a]quinolizinium chloride dihydrate and 3-[(2S)-1-methyl-2-pyrrolidinyl]pyridine, respectively.…”

“…Therefore, by definition, any comparisons we wish to make between this species and the many neutral nitrogen-containing heterocycles are beyond the scope of the present study. Domalski (our archival source, [4]) reported the enthalpy of formation of liquid nicotine to be 39 kJ mol -1 (the original source cited therein are [10]) but is 68 kJ mol -1 according to the contemporary measurements [9]). The reason for the discrepancy is not apparent; Paralleling those of the alkaloids of interest, we now give the names, formulas and structures of the unsubstituted nitrogen-containing heterocycles whose derivatives are presented in our text.…”

“…We note that none of these thermochemical studies on nicotine [9,10] compared the simultaneously calorimetrically and calculational determined enthalpies of formation for either of the following species: It appears that neither nor-nicotine nor anabasine has attracted the attention of the thermochemical community. Indeed, nicotine dominates the general discussion of tobacco-derived alkaloids and related synthetic heterocycles.…”

“…We now turn to papaverine (9). In reference [4], we find the desired thermochemical data for papaverine (systematic name 1-[(3,4-dimethoxyphenyl)methyl]-6,7-dimethoxyisoquinoline) with its solid-phase enthalpy of formation of -503 kJ mol -1 .…”

“…What about the demethoxylation enthalpies of other, but admittedly not alkaloidrelated, heterocyclic species? Let us use contemporary calorimetric studies to give us the We now turn to papaverine (9). In reference [4], we find the desired thermochemical data for papaverine (systematic name 1-[(3,4-dimethoxyphenyl)methyl]-6,7-dimethoxyisoquinoline) with its solid-phase enthalpy of formation of -503 kJ mol −1 .…”