Abwandlungsprodukte von Psilocybin und Psilocin. 2. Mitteilung über synthetische Indolverbindungen

An analytical perspective on favoured synthetic routes to the psychoactive tryptamines

“…For instance, during an investigation of the synthesis of psilocybin and psilocin derivatives, it was noted by Troxler et al that the reduction of 4-benzyloxyindole-3-yl-N,N-dimethylglyoxalylamide in THF also yielded a significant amount of the incompletely reduced ␤-hydroxy derivative (5). Complete reduction was then achieved in boiling dioxane [12]. This observation is rather interesting since these ␤-hydroxy derivatives are normally known to be synthesised by the reduction of N-1-substituted amides [13,14], which is attributed to the substituted indole nitrogen not facilitating elimination of the ␤-hydroxy group.…”

“…The LAH reduction of mono-or unsubstituted glyoxalylamides has been recognised to be more complicated, possibly due to the formation of complexes between LAH and the hydrogen atom(s) attached to the nitrogen atom [12,13,21]. For example, the so-called glycolamides 17 (␤-hydroxyacetamides) have been found during the reduction of nonsubstituted glyoxalylamides (15) (Fig.…”

“…Several modifications have led to minimising the formation of the dimeric side product, e.g. by the use of sodium instead of NaOH as the proton acceptor and excess of nitroalkane [12] or using gramine-N-oxide in the presence of sodium ethoxide [42]. A mild approach is based on the nucleophilic displacement of the quaternised aminofunction of gramine with the anion of nitroethane.…”

Beiträge zur Chemie der 4‐Hydroxyindol‐Verbindungen 10. Mitteilung über synthetische indolverbindungen [1]

“…4-Hydroxy-7-methyl-indol (lla, 1 lb) nach Schema 2 sichergestellt : 5-3,0 (3) mC (3), C (4) I 4,5 (3) (1) Verbindung 19a [19] wurde unter der Kurzbezeichnung LB 46 und dem Markennamen Visken@ als Aus der Mutterlauge kristallisierten mit Essigester 69% 2b C,H,NO [147,2] C,,H,,N,O,(262,3 05 Torr,C,,H,,NO [237,3]). Eine Losung von 181 g lb i n 1 1 Athanol wurde mit 50 g Pd/Alox (5%) und H, bis zur Aufnahnie von 1 Mol-Aqu.…”

“…((CD,),SO): 1,3 (3) t und 4,4 (2) q : CH,CH,O; 5,37 (2) 5 : OCH,-Phenyl; 6,92 (1) d (8 Hz): 5-H; 7,26 (1) 5: 3-H; 7,3-7,7 (5): 7,9 (1) [lo] ; 60% Ausbeute. CISH,,N,O,(322,4) Athanol,Cl,H17N0,(295,3), 60%.…”