Seven new bibenzyls and a dihydrochalcone from Radula variabilis

Six new bibenzyls have been isolated from the liverwort, Radula variabilis and their structures have been established by chemical and spectral evidence. In addition, a new dihydrochalcone and a new bibenzy] have been isolated as their methyl ethers. Except for two of the bibenzyls, the present compounds have a unique seven-membered heterocyclic ring and they are the first members of a new group of natural product.     

New substituted bibenzyls of Frullania brittoniae subsp. Truncatifolia

The two dihydrostilbenes, Brittonin A and Brittonin B, have been isolated from Frullania brittoniae subsp. truncatifolia (F. F. muscicola). They were identified as 3,4,5,3′,4′,5′-hexamethoxybibenzyl and 3,4,5,3′-tetra- methoxy-4′,5′,-methylenedioxybibenzyl respectively.     

Terpenoids and bibenzyls from some New Zealand liverworts

Four liverworts, Marchantia berteroana, M. foliacea, Plagiochila stephensoniana and Porella elegantula collected in New Zealand were chemically investigated. M. berteroana contains cuparene and (?)-2-hydroxycuparene as the major components. γ-Cadinene is the major component of M. foliacea. 4-Hydroxy-3′-methoxybibenzyl is a chemical marker for P. stephensoniana which belongs to the non-pungent type of Plagiochila species. P. elegantula synthesizes perrottetianal and belongs to the non-pungent type of Porella species.     

Bibenzyls from Radula tokiensis and R. Japonica

A new bibenzyl having a dihydrooxepin ring was isolated from the acetone extract of the liverwort Radula tokiensis, together with the previously known 5 bibenzyls and 3 sesquiterpenes, trans-β-farnesene, cuparene and (Jcuparenol. Two known bibenzyls were isolated from R. japonica. The bibenzyl derivatives are significant chemosystematic markers of the Radulaceae.     

Terpenoids and bibenzyls of 25 liverwort Frullania species

Twenty-five Frullania species (liverworts) were chemically investigated. Fourteen species produce allergy-inducing sesquiterpene lactones. Eighteen species contain bibenzyls. The sesquiterpene lactones and bibenzyls are obtained as the major components and they are valuable chemosystematic markers of Frullania species. On the basis of their chemical constituents, Frullania species can be divided into five chemotypes: sesquiterpene lactone-bibenzyl type; sesquiterpene lactone type; bibenzyl type; monoterpene type and cyclocolorenone type.     

New diterpenes from Porella perrottetiana

Perrottetianal A and perrottetianal B, two new diterpene dialdehydes and a new ent-labdane-type diterpene diol have been isolated from the liverwort Porella perrottetiana and their structures have been elucidated by the chemical and spectral evidence.     

Lunularic acid in cell suspension cultures of Marchantia polymorpha

Lunularic acid (LNA) was isolated from the cultured cells of the liverwort Marchantia polymorpha. Quantitative analysis by reverse phase HPLC showed that the content of LNA in the cells changed markedly during their growth, ranging from 1 to 7μg/mg dry wt. The accumulation of LNA was greatly enhanced by a deficiency of phosphate in the culture medium.     

Pinguisanin,pinguisanolide and β-pinguisenediol,three new pinguisane-type sesquiterpenes from Porella platyphylla

Three new pinguisane-type sesquiterpenes, pinguisanin, pinguisanolide and β-pinguisenediol, together with the previously known deoxopinguisone, have been isolated from a European liverwort, Porella platyphylla, and their structures have been established by the spectral evidence and some chemical transformations.     

Sesquiterpene hydrocarbons of the liverwort Scapania ornithopodioides

The liverwort, Scapania ornithopodioides, was investigated for sesquiterpene hydrocarbons by utilizing GC and GCIMS and 17 components were identified. Among these, the major component, aromadendrene, and two minor ones, cyclosativene and α-farnesene are reported for the first time as constituents of liverworts. In addition, aromadendrene also occurred in three other Taiwanese liverworts examined.     

Plagiochilines C,D, E and F,four novel secoaromadendrane-type sesquiterpene hemiacetals from Plagiochila asplenioides and Plagiochila semidecurrens

Four novel secoaromadendrane-type sesquiterpene hemiacetals, plagiochilines C, D, E and F, together with the previously known (?)-bicyclogermacrene, have been isolated from the liverwort, Plagiochila asplenioides and their structures have been spectroscopically elucidated. From Plagiochila semidecurrens plagiochilines A and C have been obtained along with (?)-bicyclogermacrene and its related sesquiterpene hydrocarbons.     

Sesquiterpenes of nine european liverworts from the genera, Anastrepta,bazzania, jungermannia,lepidozia and Scapania

The essential oils of fourteen liverwort specimens from nine species of the Jungermanniales have been examined as to their sesquiterpenes. The barbatenes prove to be present in detectable amounts in all but one species. Bazzanene is frequently found with the barbatenes and new chemical evidence does not support the previously assigned structure but is consistent with a structure diastereomeric to trichodiene. This is consistent with a biogenetic rationale for the barbatene skeleton. Anasterptene, a novel crystalline tetracyclic hydrocarbon, has been found in numerous oils, and chemical degradation established a common skeleton with myliol. The samples of genus Scapania elaborate sesquiterpenes of the enantiomeric humulene-longifolene sequence. New members of this group found are (?)-β-longipinene, (?)-longipipanol, and (+)-γ-himachalene. The related germacrene series is represented by a cadinene, (?)-α-ylangene, and (?)-sativene. A series of cis-fused selinenes have also been found, which are more closely allied to the germacrene-sativene group than to typical trans-fused selinenes. One of these selinenes is shown to be the same as the material previously designated as sibirene. Scapania undulata also elaborates (+)-α- and β-chamigrene, and a number of novel hydrocarbons of still unknown structure.     

Lunularic acid and related compounds in liverworts,algae and Hydrangea

Lunularic acid and lunularin were detected in 76 species of hepatics, but not in any of the Anthrocerotales or Algae examined. Lunularic acid, lunularin, 3,4′-dihydroxystilbene and a glycoside of lunularic acid were also identified in extracts of Hydrangea macrophylla roots, together with hydrangenol, hydrangeic acid and their glucosides.     

Novel bibenzyl derivatives and ent-cuparene-type sesquiterpenoids from Radula species

Four novel prenyl bibenzyls, perrottetin A–D were isolated from the liverwort Radula perrottetii together with a new sesquiterpene phenol, ent-2, 3-dihydroxycuparene and a prenyl dihydrochalcone, and their structures were determined by spectral methods and chemical transformations. Further investigation of the French species R. complanata resulted in the isolation of four new bibenzyls, 3, 4′-dimethoxybibenzyl, 3,5-dihydroxy-4-(2, 3-epoxy-3-methylbutyl)bibenzyl, radulanin H and radulanolide. R. buccinifera was chemically close to R. complanata. The composition of bibenzyls found in R. perrottetii and R. oyamensis were different from that of the other Radula species referred to in the section Radula. Some prenyl bibenzyls showed antimicrobial activity against Streptococcus aureus (20 μg/ml). The allergenic activity of R. complanata is due to (+)-frullanolide from the liverwort Frullania dilatata which is intermingled in R. complanata.     

Characterization of the Contents of Oil Bodies from the Liverwort Radula complanata1

Abstract: With a combination of enzymatic treatment and micromanipulation, the contents of oil bodies of Radula complanata were obtained. A GC‐MS analysis revealed that 3‐methoxybibenzyl is the main constituent of these compartments. Its structure was elucidated by NMR spectroscopy.     

Two guaiane-type sesquiterpene lactones and their related sesquiterpene lactones from Porella japonica

Two new guaiane-type sesquiterpene dilactones, porelladiolide and 3α,4α-epoxyporelladiolide and a new germacranolide, 3β-hydroxycostunolide, together with the previously known germacranolides, guaianolides, pinguisane-type sesquiterpenes, and a sacculatane-type diterpene dialdehyde have been isolated from the liverwort, Porella japonica and their structures have been established by the spectral evidence and some chemical transformations. Porelladiolide, 3α,4α-epoxyporelladiolide and the sesquiterpene with α-methylene γ-lactone group showed inhibitory activity toward the germination and growth of roots of rice in the husk.     

Isoscutellarein and hypolaetin 8-glucuronides from the liverwort Marchantia berteroana

The major flavonoid of Marchantia berteroana is hypolaetin 8-O-β-d-glucuronide. This is accompanied by apigenin and luteolin, isoscutellarein (8-hydroxyapigenin) 8-O-β-d-glucuronide, the 7-O-β-d-glucuronide and -galacturonide of apigenin and luteolin, luteolin 3′-O-β-d-glucuronide and -galacturonide, luteolin 7,3′-di-O-β-d-glucuronide and -galacturonide, luteolin 3′,4′-di-O-β-d-glucuronide and -galacturonide, luteolin 7,4′-di-O-β-d-glucuronide, and hypolaetin 8,4′-di-O-β-d-glucuronide. The isoscutellarein and hypolaetin glucuronides, and the galacturonide flavones are all new natural products.     

Sesquiterpenoids of Riccardia and Pallavicinia species

Riccardia species (Metzgeriales) contain various types of sesquiterpenes. R. jackii produces ent-selinane-, ent-aromadendrane-and ent-bicyclogermacrane-type sesquiterpenes together with (R)-cuparene and α-barbatene. Aneura pinguis (= Riccardia pinguis) is chemically quite different from R. multifida and R. jackii. The former produces a large amount of pinguisone. R. multifida contains 6-(3-methyl-2-butenyl)-indole and (+)-β-elemene as the major components. Pallavicinia longispina (Dilaenaceae; Metzgeriales) produces mainly spathulenol. The chiral properties of the sesquiterpenes isolated from R. jackii are quite similar to those of red algae, Laurencia species.     

The taxonomic position of Sphaerocarpos and Riella as indicated by their flavonoid chemistry

The major flavonoid glycosides of Sphaerocarpos texanus are luteolin 7-O-glucuronide and 7,4′-di-O-glucuronide. Riella americana and R. affinis both contain apigenin, chrysoeriol and luteolin 7-O-glucuronides but R. americana additionally contains luteolin 3′-O-glucuronide. This finding supports the inclusion of Sphaerocarpaceae and Riellaceae in the order Marchantiales rather than their separation into another order.     

Antifungal bis[bibenzyls] from the Chinese liverwort Marchantia polymorpha L

Bioassay-guided separation of the antifungal constituents of the Chinese liverwort Marchantia polymorpha L. (Marchantiaceae) led to the isolation of seven bis[bibenzyl]-type macrocycles. On the basis of NMR and MS analyses, the three new compounds plagiochin E (1), 13,13'-O-isoproylidenericcardin D (4), and riccardin H (7) were identified, together with four known compounds: marchantin E (2), neomarchantin A (3), marchantin A (5), and marchantin B (6). Their antifungal activities against Candida albicans were determined by TLC bioautography.     

Flavonoid variation in the liverwort Conocephalum conicum: Evidence for geographic races

The flavonoids of 2 samples of Conocephalum conicum gametophyte tissue have been studied, one from U.S.A. and the other from Germany. Common to both samples were vicenin-2, lucenin-2, the 7-O-glucuronides of apigenin, chrysoeriol and luteolin and the previously unknown 7-O-glucuronide 4′-O-rhamnosides of apigenin, chrysoeriol and luteolin. Additionally the German sample contained the 7,4′-di-O-glucuronides of apigenin and luteolin and a new compound, apigenin 7-O-diglucuronide 4′-O-glucuronide. The North American sample contained, additionally, luteolin 7,3′-di-O-glucuronide, luteolin 7-O-glucuronide 3′,4′-di-O-rhamnoside (a new triglycoside) and 2 further derivatives of luteolin 7-O-glucuronide. Evidence is presented for the existence of geographic faces of C. conicum and for the qualitative invariability of the flavonoid patterns with changing season or environment.