Synthese des Nicotins

Abstract

Bemerkenswerth ist noch, dass sich das aus 1-(N-) Methylindol und Phtalsiiureanhydrid durch Wasseraustritt gewonnene isomere Phtalylmethylindol, C26H90N2 02, wesentlich anders verhalt. Es krystallisirt in farblosen Prismen. Die Untersuchung wird fortgesetzt. B r e s l a t i , Chemisches Universitatslsboratorium. 189. Arne P i c t e t und A. Rotschy: Synthese des Nicotins. (Eingeg. am 14.Marz 1904; mitgetheilt in dcr Sitzung von Hm. P. Jacobson.) Die Versuche, die der Eine oon uns in Gemeinschaft mit P.9

The Stereospecificity of Nicotine

“…Free (+)-nicotine base, which we obtained from specimens of the di-(-)-hydrogentartrate dihydrate having all betwe3en -25.0 and -25.4°, had a"= + 167.60. Pictet & Rotschy (1904) found a2= + 163.20 for their purest sample of this isomer, and values of -166.4 and -168.0°for various samples of the other (natural) isomer.…”

“…Mayor's original description (Pictet & Rotschy, 1904) indicates that in the species he studied (-)-nicotine acted in a different way from (+)-nicotine, producing considerable central stimulation accompanied by respiratory paralysis, whereas (+)-nicotine was probably toxic because it paralysed breathing by desensitizing the muscle endplates of the diaphragm. How far the toxic action of (-)-nicotine was central and how far it was peripheral (and similar to that of the (+)-isomer) is not clear, but the fact that the drug can act both centrally and peripherally may well explain why in some species it is much more active than the (+)-isomer, whereas in others it is only equiactive.…”

“…This material melted at 89 to 900 C and had a17 = +25.40 (for the anhydrous salt); Pictet & Rotschy (1904) recorded a melting point 88 to 890 C, and a47 = +26.6°.…”

“…The material was recrystallized until the melting point was 89 to 90°C and a17 was -25.5°(for the anhydrous salt). The purest sample obtained by Pictet & Rotschy (1904) had a"= -25.60; if, however, it is assumed that the rotation should be the same as that of the diastereoisomer, (-)-nicotine di-(+)-hydrogentartrate dihydrate, but of the opposite sign, the material used in this work should be 97.8% optically pure. Free (+)-nicotine base, which we obtained from specimens of the di-(-)-hydrogentartrate dihydrate having all betwe3en -25.0 and -25.4°, had a"= + 167.60.…”

“…(+)-Nicotine was tested as the di-(-)-hydrogentartrate dihydrate, obtained by racemizing natural nicotine, as described by Pictet & Rotschy (1900) but with 40-g quantities in a stainless steel autoclave instead of l0-g quantities in a sealed glass tube, and resolving the racemate as described by Pictet & Rotschy (1904). The material was recrystallized until the melting point was 89 to 90°C and a17 was -25.5°(for the anhydrous salt).…”