Revised Structure of Phaeantharine

Abstract

Revised structure 8 is proposed for the quaternary bisbenzylisoquinoline alkaloid phaeantharine, based on spectrometric data. Phaeantharine, which occurs in Phaeanthus ebracteolatus (fam. Anonaceae), has current interest as a potential insecticide. Phaeantharine also exhibits moderate activity against gram-positive bacteria.

Bisbenzylisoquinoline Alkaloids

“…608.2886 Type VI (R,S) 6,7*, 11 + , 12-6,7,8*, 12 + A reevaluation of the assignment of structure as published in 1972 ( 182) demonstrated an inconsistency in the structural representation (but not the actual work) of the alkaloid (110,111) with the revelation that ( + )-thalrugosamine was in reality (+ )-homoaromoline [42] (180). MS: M+594 (41), 593 (42), 382 (21), 381 (100), 367 (14), 192(17), 191 (68), 190 (21), 174 (22), 168 (18) (175) CD: Positive tail, -5 (215), 0 (220), +27 (238), 0 (240), -14(246), -1.5 (sh) (258), 0 (275), +4…”

“…145.1 (C-8), 122.2(C-8a), 38.0(C-a), 119.9(C-9), 143.5 (C-10), 141.5 (C-ll), 152.3 (C-12), 101.5 (C-13), 121.7 (C-14), 64.1 (C-V), 44.9 (C-3'), 24.9 (C-4'), 128.1 (C-4a'X 112.0 (C-5'), 148.1 (C-6'), 149.1 (C-7'), 126.4 (C-8'), 128.1 (C-8a'X 42.3 (C-'), 133.1 (C-9'), 129.6 (C-10' 157.2 (C-l V), 120.6 (C-12'), 132.5 (C-13'), 133.1 (C-14'), 39.4 (N-2 NCH3), 40.1 (N-2' NCH3), OCH3 signals not reported (96) [Note: These assignments were based on the original structure proposed for thalibrunine (110) and not the revised structure (111)] 120 TILIAMOSINE (C36H3606N2:592.2573) MP: 167-170°( CHCI3/MeOH) (amorph.) (120) [a]25D: +267°(r=0.48, CHC13) (120) UV: 235 (sh) (4.70), 290 (3.98) NCH3 2.32, OCH3 3.83, 3.94, 3.98, ArH 6.66, 6.97 (d) (1H) <J=8.5 Hz), 7.00 (d) (1H) (/=8.5 Hz), 7.32 (dd)(lH) (/=2.2, 8.1 Hz), 7.35 (dd) (1H) (7=2.2, 8.5 Hz), 7.62(d)(lH) (1.8 Hz), 7.69 (d) (1H) (7=2.2 Hz), 8.13 (120) MS: M+ 592, 591, 366, 365, 351, 211, 183 (100) (120) DERIVATIVES: N, O-Diacetyltiliamosine (Tiliamosine+Ac20+pyridine) (120) MP: 182-184°( CHC13) (120) [a]25D: +423°(c=0.35, CHC13) (120) UV: 236 (sh) (4.59), 291 (3.79) (120) IR(KBr): 1765, 1645 (120) nmr: OCOCH3 2.13, NCH3 2.24, NCOCH3 2.24, OCH3 3.81 (s) (6H), 3.84, ArH 6.61, 6.79- 7.95 (m) (6H), 8.05 (120) MS: M+676, 634, 408, 393, 366, 365, 211, 183 (100) (120) 130 deriva...…”

“…ArH 5.97 (H-8'), 6.46 (dd)(lH)(7= 1.9, 8.2 Hz)(H-10'), 6.55 (H-5), 6.61 (d)(lH)(7= 1.8 Hz)(H-10), 6.69(H-5'), 6.66-6.73 (m)(2H)( -11' andH-13'), 6.82 (d)(1H)(7= 8.3 Hz)(H-13), 6.96 (dd) (1H) (7= 1.8, 8.3 Hz) (H-14), 7.11 (dd) (1H) (7=1.9, 8.2 Hz) (H-14') (193) 152 COCSOLINE (C34H3205N2: 548.2311) MS: M+548 (57), 547 (57), 349 (4), 335 (100), 334 (27), 321 (26), 305 (13), 168(6), 107 (4) (175) CD: Negative tail 0(215), +32 (229), 0 (251), +1(252), +9 (290), 0 (315) (175) 153 COCSULINE (C35H3405N2: 562.2468) CD: +44(239), +11 (292) (122) Negative tail, 0(214), +27 (232), +2(250), +7.3 (292), 0 (320) (175) 157 ISOTRILOBINE (C36H3605N2: 576.2624) UV: 234(4.56), 287 (3.65) (175) MS: M+576 (22), 575 (15), 349 (100), 335 (44), 319 (7), 175 (59) (175) CD: Negative tail, 0(213), +31(234), +2(251), +8(290), 0(320) (175) 161 TRICORDATINE (C34H3205N2: 548.2311) CD: Negative tail, 0 (218), +9 (234), 0 (255), +2.3 (sh) (270), +2.5 (290), 0 (310) (175) 168 REPANDULINE (C37H3607N2:620.2523) nmr: NCH3 2.40 (N-2), 2.65 (N-2'), OCH3 3.62, CH202 5.92 +5.97, A1H 2.9-3.0 (H-l), 2.9-3.05 (H-3eq), 2.4-2.6 (H-3ax), 1.95-2.15 (H-4eq), 2.3-2.5 (H-4ax), 4.15 (HA), 3.88 (HB), 2.95-3.10 ( -), 2.90-3.05 (H-a), 3.30-3.38 (H-a'), 2.63-2.73 (H-a'),…”

Antimicrobial Benzyltetrahydroisoquinoline-Derived Alkaloids from the Leaves of Doryphora aromatica

“…1 H and 13 C NMR spectra of compound 1 showed a number of paired signals, indicating a significant level of symmetry. The structure of compound 1 (Figure ) was unambiguously identified as the TFA salt of the known compound phaeantharine, an alkaloid previously isolated from Phaeanthus ebracteolatus , by comparison of the observed and reported data …”

“…The structure of compound 1 (Figure 4) was unambiguously identified as the TFA salt of the known compound phaeantharine, an alkaloid previously isolated from Phaeanthus ebracteolatus, by comparison of the observed and reported data. 18 Compound 2 (Figure 4) was isolated as a bright yellow solid, and the molecular formula for the free base of 2 was determined to be C 39 H 43 N 2 O 6 + by HRESIMS data on the [M − CF 3 COO − ] + ion at m/z 635.3108 (calcd for C 39 H 43 N 2 O 6 + , 635.3116). In the 13 C NMR spectrum of 2 (Table 1), 39 carbon signals were observed, assigned as seven methyls, of which five are part of methoxy groups (δ C 55.1, 55.9, 56.3, 57.0, and 57.2), four methylenes, including one bearing a heteroatom (δ C 44.7), one aliphatic methine bearing heteroatoms (δ C 64.3), and 27 aromatic carbons arising from four aromatic rings.…”