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Two new lignans, erythro-dihydroxydehydrodiconiferyl alcohol (1) and its threo isomer (2), were isolated from the bark of Eucommia ulmoides OLIV. (Eucommiaceae), together with six known lignans and three known phenolic compounds. Their structures were elucidated on the basis of spectroscopic analyses and chemical evidence.

A new phenlypropanoid glycoside has been isolated from the methanolic extract of the aerial parts of Stachys lavandulifolia (Lamiaceae), lavandulifolioside (1). On the basis of chemical and spectral data the structure of the new compound 1 has been elucidated as β-(3,4-dihydroxyphenyl)ethyl O-α-L-arabinopyranosyl-(12)-α-L-rhamnopyranosyl-(13)-4-O-caffeoyl-β-D-glucopyranoside.

Three new lignans, (+)-fraxiresinol [(1S, 2R, 5R, 6S)-1-hydroxy-2-(3, 5-dimethoxy-4-hydroxyphenyl)-6-(4-hydroxy-3-methoxyphenyl)-3, 7-dioxabicyclo [3.3.0] octane] (3), (+)-1-hydroxysyringaresinol (4) and (+)-1-hydroxypinoresinol-4'-β-D-glucoside (8), and five known lignans, (+)-pinoresinol (1), (+)-1-hydroxypinoresinol (2), (-)-olivil (5), (+)-cyclo-olivil (6) and (+)-pinoresinol-β-D-glucoside (7), were isolated from the bark of Fraxinus mandshurica RUPR. var. japonica MAXIM and the bark of F. japonica BLUME (Oleaceae). Their structures were elucidated on the basis of spectroscopic analysis and chemical evidence.

Negative ion mass spectra of underivatized flavonoid O- and C-glycosides were recorded using desorption chemical ionization (DCI) at a low reagent gas pressure. Advantages and limitations of the method for the characterization of the mono-, di- and triglycosides are discussed. For all O-glycosides investigated, the aglycone moieties are found to be base anions. The molecular masses of the glycosides are indicated by the presence of [M]−. ions with fairly high abundances for monoglycosides, lower abundances for diglycosides and a very low intensity for triglycosides. In addition to the sugar moiety losses, anions which resulted from the stepwise elimination of water from the sugar moiety were also observed at m/z 290 or 306 in 1 6 linked bioses, m/z 127, 145 and 163 in deoxyhexose as well as m/z 161 and 143 in hexose. Those ions except ions due to the molecule and the retro-Diels–Alder cleavage of the aglycone moiety could not be found in electron ionization mass spectra. Consequently, information concerning the structure of the aglycone moiety could be obtained using the EI technique and of sugar moiety using the negative ion DCI technique; also the combined positive and negative ion was shown to be a good approach for the structural characterization of flavonoid glycosides.

A new lignan glycoside was isolated from the bark of Eucommia ulmoides OLIV. (Eucommiaceae) and its structure was established as (+)-1-hydroxypinoresinol 4"-O-β-D-glucopyranoside (1) on the basis of chemical evidence and spectroscopic studies. An isomer of 1, (+)-1-hydroxypinoresinol 4'-O-β-D-glucopyranoside (2), was also isolated, together with (±)-erythro-, and (±)-threo-guaiacylglycerol (3 and 4), (+)-cyclo-olivil (5) and (-)-olivil (6).

The phloroglucinol derivatives of Dryopteris abbreviata (DC.) NEWMAN from Turkey, a member of the European D. filix-mas complex, were investigated. A known compound, flavaspidic acid PB (I), and three new compounds, designated as dimethylphlorobutyrophenone (II), abbreviatin PB (III) and trisabbreviatin BBB (IV), were isolated in addition to the already reported compounds, filixic acid, flavaspidic acid AB and abbreviatin BB (V). This is the first report of the occurrence of a series of phloroglucinol derivatives lacking the filicinic acid ring moiety, i.e., compounds II, III, IV and V, in European taxa of the D. filix-mas complex.

Two 2, 3-dibenzylbutyrolactone lignans containing a secondary hydroxyl group at one of the benzylic positions, 5-hydroxyarctigenin (I) and 5-hydroxytrachelogenin (XI), were transformed to phenyltetralin lignans, α-conidendrin monomethyl ether (II) and 3-hydroxy-α-conidendrin monomethyl ether (XII), respectively, by acid treatment. The hemiacetal lignan, (1S, 2R, 3S, 3aR) 6, 7-dimethoxy-3-hydroxy-2-hydroxymethyl-1-3', 4'-dimethoxyphenyl-1, 2, 3, 4-tetrahydronaphthalene-3-carboxylic acid lactol (XV), was obtained in addition to isoolivil dimethyl ether (XIV), the normal reduction product, when 3-hydroxy-α-conidendrin dimethyl ether (XIII) was treated with lithium aluminum hydride, and a mechanism is proposed for this reaction.

The structure of a new lignan glucoside isolated from the stem of Olea europaea LINN. (Oleaceae) was elucidated as (+)-1-acetoxypinoresinol-4´-β-D-glucoside [(1S, 2R, 5R, 6S)-1-acetoxy-2-(3´-methoxy-4´-hydroxyphenyl)-6-(3"-methoxy-4"-hydroxyphenyl)-3, 7-dioxabicyclo [3, 3, 0] octane 4´-β-D-glucopyranoside] by analysis of the carbon-13 nuclear magnetic resonance and circular dichroism spectra.

A component which showed tanning activities, was isolated from Rabdosia japonica , and was named rabdosiin. It was shown to be a tetramer of caffeic acid with a lignan skeleton.

The phenolic compounds in leaves of four Forsythia species were investigated. Phillygenin (1), (+)-pinoresinol (2), phillyrin (3), (+)-pinoresinol-β-D-glucoside (4), forsythiaside (11) and rutin (13) were isolated from Forsythia europaea DEGEN et BALD, arctigenin (5), matairesinol (6), arctiin (7), matairesinoside (8), acteoside (12) and 13 from F. ovata NAKAI, and (+)-pinoresinol monomethyl ether (9), (+)-pinoresinol monomethyl ether-β-D-glucoside (10), compounds 1-4, 12 and 13 from F. japonica MAKINO and F. giraldiana LIGEL.The distributions of lignans, lignan glucosides, phenylpropanoids and flavonoids in seven Forsythia species investigated so far (F. suspensa, F. viridissima, F. koreana, F. europaea, F. japonica, F. ovata and F. giraldiana) were compared.

Coumarin glucosides, esculin (1) and scopolin (2), were isolated from the bark of Olea africana MILL. (O. europaea L. subsp. africana (MILL.) GREEN) while isoscopoletin-β-D-glucoside (magnolioside) (3) was isolated from the bark of Olea capensis L. The secoiridoid glucoside oleuropein (4) was also isolated from both species.

Studies were conducted on adenosine 3', 5'-cyclic monophosphate (cyclic AMP) phosphodiesterase inhibition by lignan glucosides from bark of Eucommia ulmoides OLIV. (Eucommiaceae). Various lignan diglucosides. (+)-syringaresinol di-O-β-D-glucopyranoside (1c), (+)-medioresinol di-O-β-D-glucopyranoside (2c), (+)-pinoresinol di-O-β-D-glucopyranoside (3c) and (+)-1-hydroxy-pinoresinol 4', 4"-di-O-β-D-glucopyranoside (4d), showed strong inhibitory activity.The structure-inhibitory activity relationships of the aglycone and its glucosides are discussed. The order of inhibitory effect was diglucoside g aglycone > monoglucoside.

The effects of O-methylation and O-glucosylation on the carbon-13 nuclear magnetic resonance chemical shifts of matairesinol (1), (+)-pinoresinol (6) and (+)-epipinoresinol (11) are discussed. The chemical shifts of carbons on the 2, 3-dibenzylated butyrolactone and 2, 6-diarylated 3, 7-dioxabicyclo [3. 3. 0] octane rings are not affected by methylation and glucosylation of hydroxy groups on the aromatic rings. As regards the chemical shifts of aromatic carbons caused by O-methylation, all the 1'(1"), 3'(3"), and 4'(4") carbons of the guaiacyl unit are characteristically shifted downfield by 1.6±0.1, 1.3±0.1, and 2.4±0.1 ppm, respectively, while the 5'(5") carbons are shifted upfield by 3.5±0.1 ppm. In the case of the chemical shifts of aromatic carbons caused by O-glucosylation, all the 1'(1") and 3'(3") carbons of the guaiacyl unit are characteristically shifted downfield by 3.0±0.1 and 1.3±0.1 ppm, respectively.

The title compounds have been prepared as analytical standards for the identification of chlorpromazine metabolites in biological materials. Unequivocal structural proof of key compounds was accomplished by using at least two unrelated syntheses for each one. Resistance of some phenothiazines to preparation via classic Smiles rearrangement is discussed. More examples are offered of halogen-induced Smiles rearrangement. A rare example of phenothiazine polymorphism is presented.

As the components of the stems of Trachelospermum asiaticum NAKAI var. intermedium NAKAI, arctiin (I), matairesinoside(VI) and tracheloside(VIII) were isolated. VI was elucidated as 4, 4'-dihydroxy-3, 3'-dimethoxy-lignan-olid(9, 9')-4'-β-D-glucopyranoside. In addition the formula of VIII established by T.Takano, et al. as C36H50O18 was reexamined and revised to C27H34O12·1/2H2O. VIII gave trachelogenin(X), C21H24O7, mp 139-141° and D-glucose by acid or emulsin hydrolysis. From chemical and physical data structure of X was proposed as 4', 8'-dihydroxy-3, 4, 3'-trimethoxy-lignan-olid(9, 9')(Xa) or 4, 8'-dihydroxy-3, 3', 4'-trimethoxylignan-olid(9, 9')(Xb). In this paper structure of methyltranchelogenin(XI) with absolute configuration was determined to be 8(S), 8'(S)-8'-dihydroxy-3, 4, 3', 4'-tetramethoxy-lignan-olid(9, 9'). Now we suggest two possible structures for VIII; 8(S), 8'(S)-4', 8'-dihydroxy-3, 4, 3', -trimethoxy-lignan-olid(9, 9')-4'-β-D-glucopyranoside(VIIIa) or 8(S), 8'(S)-4, 8'-dihydroxy-3, 3', 4'-trimethoxy-lignan-olid(9, 9')-4-β-D-glucopyranoside(VIIIb).

A new lignan diglucoside was isolated from the stems of Trachelospermum asiaticum NAKAI var. intermedium NAKAI (Apocynaceae) and its structure was established as nortrachelogenin-4, 4'-di-O-β-D-glucopyranoside (I). Also the presence of α-conidendrin glucoside was suggested.

The title compounds and various derivatives have been prepared as analytical standards for the identification of chlorpromazine metabolites in biological materials. Additional evidence is presented for the existence of a halogen-induced Smiles rearrangement in the phenothiazine series.

A new lignan glucoside named nortracheloside (IV), C26H32O12·H2O, mp 95-100°, was isolated from the stems of Trachelospermum asiaticum NAKAI var. intermedium NAKAI (Apocynaceae). The lignan derivatives were prepared from tracheloside (III) and nortracheloside (IV). From the discussion of mass spectra of the lignan derivatives, the structures of III and IV were established as 8(S), 8'(S)-4', 8'-dihydroxy-3, 4, 3'-trimethoxy-lignan-olid(9, 9')4'-β-D-glucopyranoside and 8(S), 8'(S)-4, 4', 8'-trihydroxy-3, 3'-dimethoxy-lignan-olid(9, 9')4'-β-D-glucopyranoside, respectively.

A new lignan glycoside was isolated from the stems of Trachelospermum asiaticum NAKAI var. intermedium NAKAI (Apocynaceae) and its structure has been determined as 4'-hydroxy-3, 3', 4-trimethoxy-lignan-olid (9, 9')-4'-(6-O-β-D-glucopyranosyl)-β-D-glucopyranoside (=arctigenin-4/-β-gentiobioside)(V), which is a sole example of naturally occuring of lignan having glucosyl glucose moiety.

Two new lignan glucosides, (+)-1-acetoxypinoresinol 4″-methyl ether 4′-β- d -glucoside and (+)-1-hydroxypinoresinol 4′-β- d -glucoside, together with three known glucosides, (+)-1-acetoxypinoresinol 4′-β- d -glucoside, esculin and oleuropein, were isolated from the bark of Olea europaea subs africana .

A rosmarinic acid dimer named rabdosiin (1__-) was isolated from the stem of (Rabdosia japonica)___- Hara (Labiatae). Its structure was determined including the absolute configurations at four asymmetric centers.

A new dihydroflavonol glycoside, taxifolin 3-arabinoside, together with the known substances: taxifolin 3-glucoside, quercetin 3-arabinoside, taxifolin and chlorogenic acid were identified from the leaves of Trachelospermum jasminoides var. pubescens . Structural elucidation was carried out by comparison of mass spectra with those of their methylated and acetylated derivatives. Taxifolin 3-glycosides were found to be Aphanomyces cochlioides zoospore attractants.

A new anthraquinone glycoside, together with α-sorinin, has been isolated from the bark of Rhamnus pallasii and its structure elucidated as physc

A new caffeoyl glycoside of 3, 4-dihydroxy-β-phenethyl alcohol, designated as forsythiaside (1), was isolated from the fruits of Forsythia suspensa VAHL (Oleaceae). The structure of 1 is proposed to be 3, 4-dihydroxy-β-phenethyl-O-α-L-rhamnopyranosyl-(1→6)-4-O-caffeoyl-β-D-glucopyranside on the basis of analysis of the carbon-13 nuclear magnetic resonance spectrum.

Matairesinol-4′-β- d -glucoside (matairesinoside) and tracheloside have been isolated from the stem of Trachelospermum asiaticum var. intermedium . The structure of tracheloside is discussed.

A new caffeoyl glycoside of β, 3, 4-trihydroxyphenethyl alcohol, designated as suspensaside (1), was isolated from the fruits of Forsythia suspensa VAHL (Oleaceae). The structure of 1 was established as DL-β, 3, 4-trihydroxyphenethyl-O-α-L-rhamnopyranosyl-(1→6)-4-O-caffeoyl-β-D-glucopyranoside on the basis of analysis of the carbon-13 nuclear magnetic resonance spectrum and chemical evidence. Compound 1 exhibited antibacterial activity against Staphylococcus aureus TERASHIMA. with MIC 4.1 mM (2.6 mg/ml).

Four new lignans, (+)-1-acetoxypinoresinol [(1S, 2R, 5R, 6S)-1-acetoxy-2, 6-bis (4-hydroxy-3-methoxyphenyl)-3, 7-dioxabicyclo [3. 3. 0] octane] (1), (+)-1-hydroxypinoresinol (2), (+)-1-acetoxypinoresinol 4"-O-methyl ether (3) and (+)-1-hydroxypinoresinol 4"-O-methyl ether (4), and two known lignans, (-)-olivil (5) and (+)-cyclo-olivil (6), were isolated from the bark of Olea europaea L. (Oleaceae). Their structures were elucidated on the basis of spectroscopic analysis and chemical evidence. The lignans 1, 2 and 3 were also isolated from the bark of Olea africana MILL. (Olea europaea L. subsp. africana (MILL.) GREEN), and lignans 5 and 6 from the bark of Olea capensis L.

A number of lignans, including those isolated from Arctium lappa (Compositae), were subjected to Ca2+ antagonist assay. The most potent activity occurred in trachelogenin, the calculated Ic50 and pA2 of which were 1.1×10-6 M and 6.60 respectively. Tranchelogenin had a potent and long-lasting antihypertensive effect on spontaneously hypertensive rats.

Cyclic adenosine monophosphate (AMP) phosphodiesterase inhibitors contained in Forsythia suspensa were identified as lignans, (+)-pinoresinol (Ja) and (+)-pinoresinol-β-D-glucoside (Id), and their structure-activity relationship was investigated. In pinoresinol congeners, the configuration of the two phenyl rings is very important in relation to the activity. When both of the p-hydroxyl groups in matairesinol congeners are substituted by methyl or glucose, the activities are decreased as compared with those of the unsubstituted compounds.

A new phenlypropanoid glycoside has been isolated from the methanolic extract of the aerial parts of Stachys lavandulifolia (Lamiaceae), lavandulifolioside (1). On the basis of chemical and spectral data the structure of the new compound 1 has been elucidated as β-(3,4-dihydroxyphenyl)ethyl O-α-L-arabinopyranosyl-(12)-α-L-rhamnopyranosyl-(13)-4-O-caffeoyl-β-D-glucopyranoside.

Two 2, 3-dibenzylbutyrolactone lignans containing a secondary hydroxyl group at one of the benzylic positions, 5-hydroxyarctigenin (I) and 5-hydroxytrachelogenin (XI), were transformed to phenyltetralin lignans, α-conidendrin monomethyl ether (II) and 3-hydroxy-α-conidendrin monomethyl ether (XII), respectively, by acid treatment. The hemiacetal lignan, (1S, 2R, 3S, 3aR) 6, 7-dimethoxy-3-hydroxy-2-hydroxymethyl-1-3', 4'-dimethoxyphenyl-1, 2, 3, 4-tetrahydronaphthalene-3-carboxylic acid lactol (XV), was obtained in addition to isoolivil dimethyl ether (XIV), the normal reduction product, when 3-hydroxy-α-conidendrin dimethyl ether (XIII) was treated with lithium aluminum hydride, and a mechanism is proposed for this reaction.