Thomas G. Hartley

The Biochemical of Tetradium, Euodia and Melicope and their significance in the Rutaceae

Abstract From the stem and root barks of Tetradium glabrifolium (Rutaceae) benzophenanthridine alkaloids have been isolated together with furoquinoline alkaloids, coumarins and limonoids. The occurrence of the l-benzyltetrahydroisoquinolinederived benzophenanthridines adds Tetradium to the small group of rutaceous genera ( Fagaropsis, Phellodendron, Toddalia, Zanthoxylum ) known to produce alkaloids of this type. These findings support Hartleys decision to reassign taxa from Euodia (sensu Engler) into the three genera Tetradium, Euodia s. s. and Melicope and his contention that Tetradium is closely allied to Zanthoxylum and Phellodendron , with which it shares several unusual chemical characters. Hartleys re-alignment of Tetradium , which cuts across Englers sub-families Rutoideae and Toddalioideae, is therefore sustained by the known distribution of secondary metabolites, whilst available information suggests a wide disparity between the chemical profiles of Tetradium and Melicope . The chemosystematic significance of the addition of Tetradium to the 1-benzyltetrahydroisoquinoline producing genera and the potential of these taxa to have acted as a starting point for biochemical evolution within the Rutaceae is discussed.

Acetophenones and coumarins from stem bark and leaves of Melicope stipitata

Abstract Melicope stipitata has yielded six acetophenone derivatives; acronylin, evodionol methyl ether, evodionol and three novel compounds. The latter were identified as 5-acetyl-6-hydroxy-2-(2-hydroxyisopropyl)-4-methoxybenzofuran (furostipitol), (rel)-(±)-6-acetyl-3,4-dihydro-4α-ethoxy-3β-hydroxy-5,7-dimethoxy-2,2-dimethyl-2H-1-benzopyran (3-hydroxydihydropyranostipitol-4-ethyl ether) and (rel)-(±)-6-acetyl-3,4-dihydro-3β,4α-dihydroxy-5,7-dimethoxy-2,2-dimethyl-2H-1-benzopyran (3,4-dihydroxydihydropyranostipitol). 5-Acetyl-6-hydroxy-2-(2-hydroxyisopropyl)-4-methoxybenzofuran was isolated together with a small quantity of another compound, tentatively identified as its dihydrofuran analogue, namely, 5-acetyl-2,3-dihydro-6-hydroxy-2-(2-hydroxyisopropyl)-4-methoxy benzofuran. The 1 H NMR spectra of 3,4-dihydroxydihydropyranostipitol in different solvents is discussed. In addition, the furocoumarins, bergapten, phellopterin, isoimperatorin andisopimpinellin, the angular pyranocoumarin, seselin, the 8-prenylated coumarins, osthol, peroxyauraptenol and osthenon, the biscoumarin, phebalin, the lignan, sesamin, and the triterpene, isobaurenol, were obtained.

The secondary metabolites of aff. Samadera SAC-2825: An australian simaroubaceae with unusual chemistry

The phytochemical analysis of two collections of a new species (SAC-2825), tentatively assigned as aff. Samadera bidwillii (Simaroubaceae), has yielded a limonoid (limonin), a quassinoid (2′-acetoxyglaucarubin), three alkaloids [2-(10′ξ-acetoxyundecanyl)-1-acetoxymethyl-4-quinolone, 1-methoxy-10-methyl-acridan-9-one and 1,8-dihydroxyacridan-9-one] and seven bicyclo-octane type lignans [(−)-sesamin, (−)-episesamin, fargesin, neofargesin, (−)-kobusin, (−)-epieudesmin and (−)-eudesmin]. The 4-quinolone alkaloid appears to be novel. The metabolites identified are collectively typical of the Rutales, but have a biosynthetic range never previously found together in a single species. Particularly noteworthy is the co-occurrence of limonoids and quassinoids in the same plant, which is currently unique to SAC-2825.

Chemosystematics of Acradenia and general significance of acetophenones in the Rutaceae

Abstract An examination of the aerial parts of Acradenia frankliniae and A. euodiiformis (Rutaceae) has confirmed that in both species the major secondary metabolites are prenylated acetophenones. The distribution of acetophenones in the Rutaceae is reviewed and discussed in the light of present ideas regarding relationships among Malesian and Australasian genera

Alkaloids and limonoids of Tetradium trichotomum: Chemotaxonomic significance

Abstract An examination of the stem and root bark of Tetradium trichotomum (Rutaceae) has yielded the alkaloids α-allocryptopine and dictamnine and the limonoids limonin, limonexic acid and calodendrolide. The presence of the 1-benzyltetrahydroisoquinoline-derived alkaloid α-allocryptopine is further chemical evidence supporting the argument that Tetradium is closely allied to Zanthoxylum and Phellodendron .

Distribution of flavonoids, alkaloids, acetophenones and phloroglucinols in the genus Bosistoa (Rutaceae)

The leaves of six of the seven species currently assigned to the Australian genus Bosistoa (Rutacea) have been examined. Major groups of metabolites isolated were flavones and flavanones, 1,3,5-oxygenated acridone alkaloids phloroglucinols and acetophenones, all of which are further modified by the addition of 5-carbon prenyl substituents. In a recent revision Bosistoa was divided into two groups and the distribution of flavonoid aglycones is found to coincide with Group II while species in Group 1 yield acridones, phloroglucinols and acetophenones. It is suggested that secondary metabolite production in Bosistoa is best rationalized by considering a central triketide or tetraketide which through either internal cyclization (phloroglucinols, acetophenones) or condensation with anthranilic acid (acridone alkaloids) or cinnamic acids (flavonoids) can give rise to all major groups of metabolites.

A coumarin from aerial parts of Geijera paniculata

Abstract The bark and leaves of Geijera paniculata have yielded two common acidic constituents, eriostoic and eriostemoic acids, and a novel coumarin, whose structure was established on the basis of spectral data, as 5-methoxy-8-(3-methylbut-2-enyloxy)-2′,2′-dimethylpyrano-[3,2- g ]-benzopyran-2-one (trivial name, 8- O -(3methylbut-2-enyl)xanthoxyletin.

Acridone alkaloids from Bosistoa transversa

Abstract Eight acridone alkaloids were isolated from Bosistoa transversa . Three of them are novel and have been identified as 1,3,5-trihydroxy-2-(2ξ-hydroxy-3-methylbut-3-enyl)-10-methylacridan-9-one (trivial name, bosistidine), 1,3,5-trihydroxy-2-(2ξ-hydroxy-3-methylbut-3-enyl)-4-(3-methylbut-2-enyl)-10-methylacridan-9-one (bosistine) and 1,3,5-trihydroxy-4-(2ξ-hydroxy-3-methylbut-3-enyl)-yukocritine. The structures were elucidated on the basis of NMR spectral data, notably NOESY and HMBC experiments.

A xanthine alkaloid from the leaves of Bosistoa floydii

Abstract A novel xanthine alkaloid and two known flavonoids have been isolated from the leaves of Bosistoa floydii and identified as 1,3-di(3-methylbut-2-enyl)-7-methylxanthine, 5,4′-dihydroxy-3,7,3′-trimethoxyflavone and 5-hydroxy-3,3′,4′,5′,7-pentamethoxyflavone.

Brombyins from the stem bark of Brombya platynema

Abstract In addition to the previously reported brombyin-I and brombyin-II, four further novel brombyin type derivatives have been obtained from the stem bark of Brombya platynema . These were identified as ( rel )-3β-piperonyl-4β-acetyl-3,4,4aβ,5,6,7,8,8aα-octahydronaphthal-1-ene (brombyin-III), ( rel )-3-piperonyl-4β-acetyl-1,4,4aβ,5,6,7,8,8aα-octahydronaphthal-2-en-1-one (brombyin-IV), 1-piperonyldodecan-9-ol-11 one (brombyin-V) and ( rel )-3β-piperonyl-4β-acetyl-2,3,4,4aβ,5,6,7,8-octahydronaphthalen-1(8a)-en-2α-ol (brombyin-VI). Also present were the simple cinnamic acid derivatives ( E )-piperonylprop-2-enal and ( E )-piperonylprop-2-enoic acid. A possible route for the formation of the brombyins is discussed.