Search

From the fraction of quaternary alkaloids of the aerial part of Glaucium oxylobum BOISS. et BUSHE (-)-trans-N-rnethylcanadinium iodide was isolated as the main alkaloid after conversion to iodides, and, in a smaller amount, (+)-N-methylcorydinium iodide, detected for the first time in Papaveraceae, further (-)-trans-N-methylstylopinium iodide, magnoflorine iodide and a new quaternary alkaloid, N-methyldomesticinium iodide, isolated for the first time as a natural substance. In the roots, magnoflorine iodide accompanied by (+)-N-methylcorydinium iodide represented the main component of the quaternary fraction. From both plant parts corytuberine was also isolated for the first time. In the tertiary fraction of alkaloids (+)-corydine, protopine and allocryptopine were the major components, accompanied by smaller amounts of sanguinarine, chelerythrine, chelirubine, domesticine, isoboldine and scoulerine. In the fraction of quaternary protoberberines coptisine, berberine and traces of corysamine were detected.

2-Methylpapaverinium iodide (I), 2'-hydroxymethyl-2-methylpapaverinium iodide (IX), and 2-methyl-3,4-dihydropapaverinium iodide (X. CH3I) form pseudobase by addition of hydroxide ions to the C(1)=N(+) bond. 2'-Hydroxymethyl-2-methyl-3,4-dihydropapaverinium iodide (XV) and 2'-hydroxymethyl-2-methyl-9-oxo-3,4-dihydropapaverinium iodide (XVI) react with hydroxide ions in aqueous medium under formation of cyclic pseudobases XVII and XVIII. The equilibrium constants (KR+) of pseudobase formation have been measured in aqueous ethanol (1 : 1 w/w, 25°C, ionic strength 0.1). The quaternary papaverinium derivatives are metabolized to isoquinilones and carbonyl compounds by means of rat liver enzymes. The role of pseudobases in these biotransformations has been discussed and biogenetic conclusions have been drawn.

From the strongly polar fraction from the tubers of Corydalis solida (L.) SW., a new quaternary alkaloid, (+)-N-methyllaudanidinium iodide, was isolated after conversion to iodides. Mass spectrometric behaviour of this type of quaternary alkaloids is described. In the tubers (0.37% of alkaloids) the main alkaloid component is (+)- and (±)-tetrahydropalmatine; other dominant alkaloids include protopine, (+)-corydaline, allocryptopine, dehydrocorydaline and jatrorrhizine. (±)-Corybulbine, (+)-corypalmine, (-)-isocorypalmine, (-)-scoulerine, (-)-stylopine, corysamine, palmatine, (+)-N-methyllaudanidinium hydroxide, (-)-cis-N-methylcanadinium hydroxide and cis-N-methylstylopinium hydroxide represent minor alkaloids. The last three mentioned were isolated in the form of iodides. Bulbocapnine, coptisine, berberine and columbamine were detected in trace amounts. The main alkaloid of the aerial parts of the plant (0.35% of alkaloids) is berberine, accompanied by coptisine, (-)- and (±)-canadine, (-)-stylopine, isoboldine, protopine, columbamine and (-)-cis-N-methylcanadinium hydroxide (isolated in the form of iodide) as significant components. Among minor alkaloids allocryptopine, (-)-isocorypalmine, (+)-corypalmine, (±)- and (-)-tetrahydropalmatine, corysamine, dehydrothalictricavine, palmatine and cis-N-methylstylopinium hydroxide (as iodide) were isolated and trace amounts of jatrorrhizine and bulbocapnine were detected.

From the leaves of Strempeliopsis strempelioides K. SCHUM. (Apocynaceae), an indigenous species from Cuba, the following alkaloids were isolated: (+)-Demethylaspidospermine, (-)-aspidosine, (+)-tubotaiwine, (-)-vallesine, (+)-condylocarpine and (+)-eburnanomine. From stem bark of the plant the following alkaloids were isolated: (-)-Aspidospermine, (+)-deacetylaspidospermine, (+)-vincadifformine, (_)-apparicine, (+)-tubotaiwine, (+)-condylocarpine and (+)-demethylaspidospermine. All the structures were proposed on the basis of spectral evidence and chemical reactions.

A new quaternary alkaloid, (-)-β-N-methylisocorypalminium hydroxide, was isolated from Glaucium squamigerum KAR. et KIR. in the form of iodide. In addition to the alkaloids already known to occur in this plant, i.e. allocryptopine (the main alkaloid), protopine, chelerythrine, sanguinarine, corydine, coptisine and berberine, additional alkaloids, i.e. (-)-chelidonine, (±)-chelidonine (diphylline) and chelirubine were also isolated from the non-quaternary fraction, while from the fraction of quaternary alkaloids (-)-β-N-methylcanadinium iodide (the second main alkaloid), (-)-α-N-methylcanadinium iodide and (-)-β-N-methylstylopinium iodide were isolated after conversion of the salt to iodides. Further the presence of small amounts of stylopine, canadine, scoulerine, corysamine, corytuberine, magnoflorine, α-N-methylstylopinium hydroxide and β-N-methyltetrahydropalmatinium hydroxide were also detected.

From the roots of STREMPELIOPSIS STREMPELIOIDES K. Schum. (Apocynaceae), the following alkaloids were isolated: (+)-pleiocarpamine, (-)-aspidospermine, (+)-eburnamonine, (+)-tubotaiwine, (+)-haplocidine, (-)-vallesamidine, (+)-tubotaiwine N-oxide, (-)-strempeliopine ( 1A) and a bisindolic base (+)-strempeliopidine ( 2). Another bisindole alkaloid of composition C 38 H 46 N 4 was isolated in minute quantity. The structures were established on the basis of spectral and chemical evidence.

Two new alkaloids, pseudorine (Ia) (quaternary benzyltetrahydroisoquinoline type) and pseudoronine (II) (benzil type), were isolated from the roots of Papaver pseudo-orientale (FEDDE) MEDW. This is a first occurrence of this type of alkaloids in Papaveraceae. The main component of the tertiary alkaloid fraction was isothebaine accompanied by smaller amounts of orientalidine, mecambridine, bracteolidine, nuciferine, protopine, and allocryptopine. The presence of salutaridine and papaverrubine D was established. Traces of coptisine and palmatine were also found in some samples. Strongly polar portion of the extract was converted to iodides. N-Methylisothebainium iodide (IIIa) (major component), pseudorine iodide (Ia), and corytuberine hydriodide (IV) (significant amounts), a minor alkaloids such as alborine iodide (alkaloid PO-5), pseudoronine (II), and magnoflorine iodide (IIIb) were isolated from this source. Structure of pseudorine was determined by UV, IR, 1H, and 13C NMR spectroscopy and using the correlation with laudanosine and codamine. Proposed structure of pseudoronine is based on the mass spectra comparison.

In addition to the alkaloids previously found in the aerial part of P. atlanticum BALL, viz. protopine, rhoeadine (predominant constituents), rhoeagenine, stylopine, cryptopine, sanguinarine, magnoflorine and papaverrubines A, B, E and D, we have now isolated the tertiary bases isothebaine, scoulerine, corytuberine and a new quaternary alkaloid 13β-hydroxy-N-methylstylopinium hydroxide (I). The presence of papaverrubine B and muramine was also detected (TLC). The contents of the bases in the roots of P. atlanticum were found similar to those in the aerial part. Magnoflorine was isolated from the roots in a considerable yield. The dominant alkaloids isolated from P. glaucum BOISS. et HAUSKN. were glaudine and glaucamine; they were accompanied by protopine, papaverrubine B and traces of sanguinarine, coptisine and papaverrubine C. Magnoflorine and corytuberine have been isolated from this species for the first time and the presence of allocryptopine, cryptopine, corydine, isocorydine and papaverrubines D and H has been demonstrated.

From Papaver albiflorum subsp. austromoravicum KUBÁT berberine and (-)-α-canadine methohydroxide (in the form of iodide) were isolated as the main alkaloids, and allocryptopine, corytuberine and small amounts of protopine, rhoeadine and canadine as the minor components. Negligible amounts of mecambrine, thebaine, aporheine (?), corydine, isocorydine, scoulerine and traces of papaverrubines A, C, D and E, coptisine, corysamine, magnoflorine, α-stylopine methohydroxide and aporheine methohydroxide were also detected. P. albiflorum PACZ. subsp. albiflorum contains thebaine almost exclusively, accompanied by trace amounts of berberine, corytuberine, protopine (?), thebaine methohydroxide and aporheine methohydroxide. From P. lecoquii LAMOTTE berberine and corytuberine were isolated as the main alkaloids, as well as small amounts of protopine, a new alkaloid (-)-hexahydromecambrine-B, allocryptopine, rhoeadine and cryptopine. The presence of isocorydine and trace amounts of canadine, stylopine, mecambrine, papaverrubines A, C, D and E, corydine, scoulerine, coptisine, magnoflorine and α-stylopine methohydroxide was also detected.

Two new quaternary alkaloids, N(1)-methyl-2β,16β-dihydroakuammicine N(4)-methochloride and epipleiocarpamine N(4)-oxide, were isolated from the leaves of Vinca minor L. Their constitution and configuration were established on the basis of spectral evidence and correlation.

A total of 29 associate components were identified in technical 9,10-anthraquinone. The product contained all the prominent impurities present in the starting anthracene except for 9,10-dihydroanthracene and fluorene. 9-(9'-Anthryl)-carbazole and Diels-Alder type adducts of anthracene with maleic anhydride and with maleinimide were also detected. The isolated and identified by-products of oxidation of anthracene were 1,4-anthraquinone, 4,4'-dioxo-1,1'-bianthrylidene, 4,10'-dioxo-1,9'-bianthrylidene, 1-(4'-oxy-1'-naphthylidene)-4-oxyanthracene, 2,3-naphthalenedicarboxylic acid and anhydride, and 5,7,12,14-tetrahydro-5,14;7,12-di(o-benzeno)pentacene-6,13-dione. Of the compounds formed by oxidation of the anthracene impurities, isolated and identified were dibenzo[b,d]pyrone, xanthone, 1,8-naphthalenedicarboxylic acid anhydride,9-fluorenone, and naphthol[2,3-b]thiophene-4,9-dione. As products of a deeper oxidation of the starting compounds, phthalic anhydride, maleic anhydride, maleinimide, phthalic acid, and maleic acid were found. Four additional components whose structure could not be determined were also isolated. The pathway of the anthracene oxidation is suggested.

From the endemic Cuban species Rauvolfia salicifolia GRISEB nine alkaloids were isolated of which the following seven had been already described: (+)-ajmalidine (I), (-)-reserpiline (II), (-)-isoreserpiline (III), (-)-isocarapanaubine (IV), (-)-ajmalicine (V), (+)-vellosimine (VI), and (+)-yohimbine (VII). The structure of (-)-raucubaine (VIII) had been previously determined by X-ray diffraction and the structure of the alkaloid (-)-raucubainine (IX) was suggested on the basis of its conversion to (-)-raucubaine (VIII). The absolute configuration of (-)-raucubaine and (-)-raucubainine was elucidated by CD spectroscopy.

Spectral data and degradations were used to determine the structure of arenophthalide A, a glycoside of the formula C19H24O9, isolated from the roots of Helichrysum arenarium. Structure I was assigned to the compound.

Cleavage with cyanogen bromide was employed to investigate the N-terminal amino acid sequence of the λ-chains of normal porcine immunoglobulin. The N-terminal homoserine-containing nonapeptide was isolated from all fractions of the λ-chains in a yield of 60% of theory. Its amino acid sequence was determined by mass spectrometry and was found to be uniform. Other homoserine-containing fragments were obtained from the cyanogen bromide hydrolyzate of the λ-chains with split disulfide bonds. Partial amino acid sequence of these fragments provided evidence that methionine in position 9 is present in more than 60% of variants and obviously has an invariant character. Variants of the λ-chains exist (by estimate not more than 15% of the total λ-chains) which, in addition to the invariant methionine residue in position 9, possess a variable methionine residue in the section between positions 46 and 51. The data obtained indicate that the sequence of 23 amino acid residues from the N-terminus of porcine λ-chains is uniform with the exception of a single replacement (in position 13). Moreover, in comparison with the sequence of λ-chains of man, mouse and birds, the sequence displays several species-specific replacements and a deletion of threonine which occupies position 5 in the chains of the other species. In the pig, the λ-chains represent the predominant type of light chains (some 70%). Hence it follows that some 50% of the light chains in this species possess a uniform amino acid sequence in the N-terminal section. These facts are difficult to reconcile with the germline theories of genetic control so that mechanisms of somatic diversification of immunoglobulins must be envisaged.

Aus Polypodium vulgare L. wurde ein Saponin, das Polypodosaponin (1), isoliert. Es geht bei der Isolierung mit Methanol leicht in das 26-O-Methyl-polypodosaponin (2) uber, an dem vorwiegend die Konstitution aufgeklart wurde. Dem zugehorigen Aglykon (26-O-Methyl-polypodogenin) konnte die Struktur eines 3β-Hydroxy-26ξ-methoxy-22ξ.26ξ-epoxy-6-oxo-5α-cholestens-(7) (4) zugeordnet werden. Im Saponin 2 ist die 3β-Hydroxygruppe an einen α-L-Rhamnopyranosyl-(1 -2)-β-D-glucopyranosyl-Rest gebunden. 2 besitzt typische Saponineigenschaften und stellt eine neue Variante der Steroidsaponine dar.