Lupinen‐Alkaloide, XVII. Konfigurationsbestimmung von Hydroxychinolizidin‐Abkömmlingen

Abstract

Zusatz von Kaliumcarbonat wurde die Base in Methylenchlorid aufgenommen und der Eindampfriickstand destilliert. Sdp. 140-1 SO", Ausb. 225 mg. Pikrut des 0-Acernts, Schmp. 164" (aus Athanol). C8HlsN02.CbH3N~07 (344.3) Ber. C 43.53 H 4.70 N 14.51 Gef. C 43.64 H 4.81 N 14.81 Azohettzolrarhunsuureesfer: Rote Kristalle aus Petrolather vom Schmp. 104". 1R-Spektrum : )N-CHj 2790, -.COOR 1730/cm. ClqH21N302 (323.4) Ber. C 70.56 H 6.54 N 13.0 Gef. C 70.98 H 6.98 N 12.9 C!.cluiiextitiol-uzuberrzolcarbuttsaureesrer: Orangefarbene Kristalle, Schmp. 89.5". 2-Hydrux,v-chir~olizidin ( VI rrrtd V l l j : I .7 g V 7 ) wurden in 20 ccm Eisessig mit 50 mg Platinoxyd hydriert. Uas Hydrierungsprodukt nahm man in Petrolather auf und chromatographierte an 150 g Aluminiumoxyd (neutral, Akt.-Stufe IV). Mit Ather/Petrolather (1 : 1) eluierte man die Base VI, die aus Petrolather farblose Kristalle vom Schmp. 103 -104" bildet; Ausb. I80 mg. IR-Spektrum s. Abbild. 2.

Rearrangement of isoxazoline-5-spiro derivatives. Part 3. Indolizine, quinolizine and pyrido[1,2-a]azepine derivatives by sequential rearrangement-annulation

“…Column chromatography (using methylene dichloride-light petroleum (3: 1) as eluant afforded the adduct (3b), R, 0.26 (963 mg, 46%), as an oil, purified by repeated column-chromatography using light petroleum-thy1 acetate ( 5 : 1) as eluant, R, 0.30 (Found: C , 46.4; H, 5.9; N, 6.4. C,H,,BrNO requires C, 46.6; H, 6.1; N, 6.0%); v,,,,(neat) 3 005, 2 955, 1 620, 1435, 1 225, and 1010 cm-'; 6,(90 MHz) 3.42 (2 H, t, J 6), 2.99 (2 H, s), 2.42 (2 H, t, J 7), 2.15-1.55 (4 H, m), 1.25-4.95 (2 H, m), and 0.9G0.60 (2 H, m); 6, 158.87 s, 64.71 s, 41.89 t, 32.99 t, 31.77 t, 27.24 t, 24.42 t, and 11.45 t (2 C); m / z 233 (0.6%), 231 (M', 0.5), 175 (2), 152 (2), 135 (8), 124 (5), 110 (3), 96 (9), 82 (12), 68 (6), 55 (49), and 42 Some 3,4-bis(4-bromobutyl)-1,2,5-oxadiazole 2-oxide [a substituted furoxan, dimer of (1 b)] was also collected, R, 0.31, as an oil; v,,,,(neat) 2 940, 2 860, 1 605, 1 470, and 1 430 cm-'; 6,(90 MHz) 3.65--3.30 ( (100).…”

Methods in alkaloid synthesis. Imino ethers as donors in the Michael reaction

“…Purification by preparative TLC provided 272 mg (60.2%) of pale yellow oil having a Rf 0.36 with two elutions of chloroform: ir (CCI4) 1672 and 1655 cm-1; NMR (CCI4) 4.63 (2 H, b s), 3.50 (3 H, s), 3.35 (2 H, m), 2.0 (3 H, m), 1.70 (3 H, b s) superimposed upon multiple! centered at 1.6 (6 H); mass spectrum m/e (% rel intensity) 181 (2), 167 (11), 162 (20), 155 (48), 126 (85), 124 (30), 123 (15), 113 (88), 112 (100), 111 (16), 110 (34), 109 (15), 99 (14), 98 (24), 91 (53), 84 (37), 81 (30), 69 (37), 68 (55), 67 (34), 65 (18), 56 (18), 55 (70), 53 (18), 41 (76); mol wt (caled forCnH19NO, 181.1467) 181.1466.…”

Azabicyclic Alcohols. II. Chemical and Catalytic Reduction of the Ketoquinolizidines1

“…At^-Ketoquinolizidine was prepared according to the published procedure. 24 The amino ketone (m.p. 80-81°) was recrystallized from ether and gave an ultraviolet spectrum which coincided with that of the previous report.…”