The Alkaloids of Thalictrum foliolosum

Abstract

Trimethylsparsiflorine (1), a new apoiphine alkaloid; known tertiary alkaloids thalicarpine (3), thalidasine (4), thalrugosidine (5) and reticuline (6); and the quaternary alkaloids magnoflorine, berberine and palmatine were isolated from the rhizome of Thalictrum foliolosum DC.Thalictrum foliolosum DC. (Ranunculaceae), a tall perennial herb, is one of the seven species of genus Thalictrum found in India (1). Extracts of the roots of the plant have been used by the natives in many ailments (1,2). The quaternary alkaloids, magnoflorine (3,4), jatrorrhizine (5), berberine (5), and palmatine (5) were isolated earlier from the plant. Thalictrum species have been known to produce a variety of alkaloids of chemical and biological interest (6-11). The alcoholic extract of the leaves, stems, and roots of T. foliolosum exhibited spasmolytic activity in a broad biological screen (12). This activity was concentrated, in the follow up studies, in the alkaloidal fraction of the extract. This prompted us to reinvestigate the alkaloidal constituents of T. foliolosum. The investigation resulted in the isolation of a new aporphine alkaloid, N,0,0-trimethylsparsiflorine (1), two known bisbenzylisoquinoline alkaloids, thalidasine (4) and thalrugosidine (5), one 1-benzylisoquinoline aporphine alkaloid, thalicarpine (3), one 1-benzyltetrahydroisoquinoline alkaloid, reticuline (6), two protoberberine alkaloids, berberine and palmatine and a quaternary aporphine alkaloid, magnoflorine. The tertiary alkaloids (3), ( 4), ( 5) and ( 6) were isolated for the first time from this species, whereas the quaternary alkaloids had been previously isolated from the rhizome of the plant., , -Trimethylsparsiflorine (1) was assigned the molecular formula C20H23O3N on the basis of high resolution mass spectrometry. The ir spectrum of the base (v max. 1600, 1560, 1490, 1360 and 1210 cm-1)in conjunction with its uv spectrum (X max. 216, 274 and 298 nm, no change in alkali) suggested the presence of an aporphine system in the molecule.The nmr spectrum of the base integrated for 23 protons. A signal at 2.30 (s, 3H) was assigned to one N-methyl group. The signals for three aromatic methoxyl groups were at 3.49 (s, 3H), 3.64 (s, 3H) and 4.00 (s, 3H), respectively. In the aromatic region there were four protons. A singlet at 6.32 was assigned to C-3 proton. A double doublet for an ortho and meta coupled proton centered at 6.54 (dd, = 8.0 and /2 = 2.0 Hz) was due to the proton at C-9. A doublet for one proton at 6.86 (d, 7 = 8.0 Hz) was assigned to an ortho coupled proton at C-8. The characteristic low field signal for the C-l 1 proton appeared as a doublet at 7.74 (d, 7 = 2.0 Hz). In the mass spectrum of the base, the molecular ion peak appeared at m/e 325 (M+). Other significant peaks in the mass spectrum were at m/e 324 (M+-1), 310 (M+-15), 294 (M+-31) and 282 (M+-43). The mass fragmentation pattern of the base was that of aporphine alkaloid type (13).The base remained unchanged on treatment with Ac20/pyridine or diazomethane. When refluxed with CH3I, it f...

Altitudinal variation of berberine, total phenolics and flavonoid content in Thalictrum foliolosum and their correlation with antimicrobial and antioxidant activities

“…There exists a compelling evidence about the increasing pressures caused by herbivores at lower elevations; hence the increase in alkaloid content may be regarded an obvious defense measure adopted by the plants at lower elevations [28] , [31] . Berberine is one of the major alkaloid reported in TF [13] ; hence a correlation between the berberine content and related medicinal properties would be helpful in setting the quality parameters of the plant. The berberine content in TF varied inversely with altitude in all type of extracts i.e.…”

“…The chemical constituents viz. berberine, columbamine, jatrorrhizine, oxy berberine, thalifendine, palmatine, thalidasine, dehydrodiscretamine, tembetarine, xanthoplanine, and magnoflorine were reported from the root of this plant [13] , [14] . Berberine, a tetra isoquinoline alkaloid has been used as the traditional medicine of India, China and North America [15] .…”

Bisbenzylisoquinoline Alkaloids

“…NCH3 2.57 (N-2'), 3.53 (N-2), OCH3 3.85, 3.90 (6H), OH 4.08 (br), A1H 5.65 (1H), ArH 6.10-7.52 (15) BC nmr: 25.6 (t, C-4'), 35.4 (t), 35.8 (t), 42.3 (q, N-2' CH3), 45.6 (t, C-3'), 46.2 (q, N-2 CH3), 55.9 (q, OCH3), 56.2 (q, OCH3), 56.2 (q, OCH3), 63.9(d, C-l'), 100.8(d), 112.1(d), 112.2 (d), 119.4(d), 119.4(s), 121.4(d), 121.5(d), 123.0 (s), 123.1(d), 127.0 (s), 127.4 (s), 128.3 (s), 129.7(d), 129.8 (s), 132.0(d), 135.0 (s), 138.5 (s), 143.4 (s), 148.3 (s), 148.6 (s), 149.0 (s), 150.0 (s), 155.5 (s), 162.5 (s) (15) MS(FD): M+605 (15) DERIVATIVES: Limacine (S,S) (Berbacolorflammine+NaBH4) (15) Trideuterioberbacolorflammine (Berbacolorflammine+NaBD4 in C2H50D+D20) (15) 219 COLORFLAMMINE (1,2,3,4-Tetradehydrolimacusine) (C37H3706N2: 605.2652) TLC: 0.48 (Si gel, CHCl3-MeOH-NH4OH [14:5:1]) and stained with iodoplatinate reagent (15) Extinction at 254nm and orange fluorescence at 366nm (15) [ot]20D: + 1050°(t=0.06, CHC1}) (15) UV: 233, 292, 333, 439 (15); 244, 267, 326, 374 (acidic Me3OH) (15) IR: (KBr) 3410, 2910, 1492 (15) nmr:…”

“…NCH3 2.45 (N-2), 3.86(N-2'), OCH3 3.86,4.01,4.08, OH4.34(br), A1H4.74(1H), 5.92 (1H), ArH 6.04-7.71 (15) BC nmr: 25.1 (t, C-4), 35.9 (t), 37.6 (t), 42.0 (q, N-2 CH3), 46.2 (q, N-2' CH3), 47.5 (t, C-4), 55.5 (q, OCH3), 55.8 (q, OCH3), 56.0 (q, OCH3), 62.6 (d, C-l), 102.3 (d), 110.7 (d), 111.1 (d), 112.0(d), 116.1(d), 120.0(d), 122.2(d), 122.9(d), 123.6(d), 123.6(d), 124.1(d), 126.2(d), 126.2 (s), 129.4 (s), 129.6 (s), 130.6(d), 131.2(d), 132.6 (s), 134.5 (s), 143.4 (s), 146.5 (s), 147.3 (s), 148.7 (s), 149.1 (s), 153.3 (s), 153.7 (s), 161.6 (s, C-l') (15) MS (FD): M+605 (15) DERIVATIVES: Limacusine (S, S) (Colorflammine + NaBH4) (15) Trideuteriocolorflammine (Colorflammine +NaBD4 in C2H50+D20) (15) Mahonia repens (Lindl.) G. Don (Berberidaceae) (16) Pseudoxandra aff.…”

Dimeric Aporphinoid Alkaloids, II

“…Thalictrum minus (6) Thalictrum revolutum (46) 10 Thalicarpine(Thaliblastine)a Sources: Thalictrum alpinum (48) Thalictrum foliosum (4) Thalictrum minus (6,25,31,37) Thalictrum revolutum (46) 15 Thaliadanine…”