Water-Soluble Constituents of Dill

Abstract

Dill [Anethum graveolens L.; Umbelliferae] has been cultivated in Europe since antiquity and used as a popular aromatic herb and spice. Its fruit has also been used for medicinal purposes in the relief of digestive problems and to stimulate milk for nursing mothers.1) Dill water was believed to have a soothing effect on the digestive system and was given to babies to relieve hiccups and colic. The fruit contains essential oil (3-4%) rich in d-carvone (main; 50-60%), and trans-and cis -dihydrocarvone, trans-and cis-carveol, limonene, d-dihydrocarveol, l-dihydrocarveol, a-and g-ter-pinene, a-phellandrene, b-terpineol, terpinene-4-ol p-cymene, thymol, carvacrol et al. were reported as other constituents. 2)However, only dillanoside has been published as a constituent of the water-soluble portion of this fruit.3) In continuation of our studies on the water-soluble constituents of spices, 4) and to show the relationship between the essential oil and the water-soluble constituent, we undertook a detailed investigation of this fruit. In this paper, we discuss the isolation and structure elucidation of monoterpenoids, monoterpenoid glycosides, aromatic compound glycosides, alkyl glycosides, glucides and nucleosides.The commercial dill was extracted with 70% methanol, and the methanolic extract was suspended in water and successively extracted with ether and ethyl acetate. The aqueous layer was chromatographed on Amberlite XAD-II to give water and methanol eluate fractions. These fractions were chromatographed on Sephadex LH-20, and subjected to a combination of silica gel, Lobar RP-8 column chromatography and HPLC to separate monoterpenoid ketodiols (1 to 2), monoterpenoid glycosides (3 to 10) and aromatic compound glycosides (11 to 17) from the methanol eluate fraction, and three alkyl glycosides (18 to 20), eleven glucides (21 to 31) and two nucleosides (32, 33) from the water eluate fraction. Among them, 2-4, 6-8, 10, 11 and 18 are new compounds. All new glucosides described in this paper were b-Dglucopyranosides as shown by their 1 H-and 13 C-NMR data (Tables 1, 2 ϩ ion peak at m/z 167 in the positive FAB-MS. The glycoside 3 was hydrolyzed with hesperidinase and, from the hydrolyzed mixtures, 1 and D-glucose were obtained. Consequently, 3 was a monoglucoside of 1. The position of the b-glucosyl unit was proved to be C-9 by the down-field glycosylation shift of the C-9 (by 8.1 ppm) signal and up-field glycosylation shift of the C-8 (by 0.7 ppm) signal, and from the observed nuclear Overhauser effect (NOE) interaction between the glucosyl H-1/H 2 -9 in the nuclear Overhauser and exchange spectroscopy (NOESY) spectrum of 3. So, 3 was characterized as (4S,8S)-8,9-dihydroxy-8,9-dihydrocarvone 9-O-b-D-glucopyranoside.Monoterpenoid ketodiol 2 (C 10 H 18 O 3 , an amorphous powder, [a] D 21 Ϫ23°) showed an [MϩH] ϩ ion peak at m/z 187 and was suggested to have one tert-methyl, one sec-methyl, one hydroxymethyl, three methylenes, two methine, one oxygenated quaternary carbon and one carbonyl group by the 1 H-and 13 C-NMR ...

Bioactive Constituents from Chinese Natural Medicines. XXVIII. Chemical Structures of Acyclic Alcohol Glycosides from the Roots of Rhodiola crenulata

“…The EtOAc-soluble fraction was subjected to normal-phase and reversed-phase column chromatographies and finally to HPLC to give three known compounds, trans-caffeic acid (17, 0.036%), 14) p-tyrosol (19, 0.3183%), 15) and kaempferol (23, 0.0068%). 16) The n-BuOH-soluble fraction was also subjected to normal-and reversed-phase column chromatographies and HPLC to give creosides I (1, 0.0026%), II (2, 0.0011%), III (3, 0.0002%), IV (4, 0.0014%), and V (5, 0.0015%), together with 18 known compounds, kenposide A (6, 0.0195%), 17) rhodioloside E (7, 0.0058%), 18) isopentenyl-3-O-b-D-glucopyranoside (8, 1.8171%), 19) n-hexyl-b-D-glucopyranoside (9, 0.0005%), 20) rhodiooctanoside (10, 0.0017%), 12) coniferoside (11, 0.0027%), 21) dihydroconiferin (12, 0.0001%), 22) icariside D2 (13, 0.0026%), 23) 4-hydroxybenzyl b-D-glucopyranoside (14, 0.0004%), 24) triandrin (15, 0.0127%), 25) vimalin (16, 0.0017%), 25) 1-O-b -D-(6Љ-O-galloyl)glucopyranoside (18, 0.0020%), 26) 2-phenylethyl b -D-glucopyranoside (20, 0.0049%), 27) salidroside (21, 1.1063%), 28) 2-phenylethyl Oa -L-arabinopyranosyl(1→6)-b -D-glucopyranoside (22, 0.0027%), 13) pollenitin (24, 0.0010%), 29) rhodosin (25, 0.0295%), 30) and clemastanin A (26, 0.0018%). 31) Creoside I (1) was isolated as a colorless amorphous powder with negative optical rotation ([a] D 27 Ϫ38.7°in MeOH).…”

“…In the positive-ion fast atom bombardment (FAB) MS of 1, a quasimolecular ion peak was observed at m/z 327 (MϩNa) ϩ . High-resolution (HR) FAB-MS analysis revealed the molecular formula of 1 to be C 14 H 24 O 7 . Acid hydrolysis of 1 with aqueous HCl 1.0 M liberated D-glucose, which was identified in HPLC analysis using an optical rotation detector.…”

Water-Soluble Constituents of Coriander.

“…4) However, to the best of our knowledge no report has been published on the constituents of the water-soluble portion of this fruit. In a continuation of our studies on the water-soluble constituents of spices, 5) and to show the relationship between the essential oil and the water-soluble constituent, we undertook a detailed investigation of this fruit. In this paper, we discuss the isolation and structure elucidation of monoterpenoid alcohols and its glucosides, norcarotenoid glucosides, an aromatic compound and its glycosides, alkyl glucosides, glucides, uracil, and nucleosides.…”

“…The aqueous layer was chromatographed on Amberlite XAD-II to give water and methanol eluate fractions. The methanol eluate fraction was chromatographed on Sephadex LH-20 and then subjected to a combination of silica gel, Lobar RP-8 column chromatography, and HPLC to separate two monoterpenoid triols (4,5), seven monoterpenoid glycosides (1 to 3, 6 to 9), three norcarotenoid glucosides (10 to 12), an aromatic compound (17), seven aromatic compound glycosides (13 to 16, 18 to 20), two alkyl glucosides (21,22), eight glucides (23 to 30), uracil (31), and two nucleosides (32, 33). Among them, 2 to 9, 18, and 19 are new.…”

Spasmolytic Potential of Some Medicinal Plants Belonging to Family Umbelliferae: A Review

“…The purpose of this study was to determine the spasmolytic potential of Anethum graveolens seeds essential oil. Dill (Anethum graveolens) is popular aromatic herb and spice 11 . Its fruits have been used for medicinal purposes in the relief of digestive problems and to stimulate milk for nursing mothers 12 .…”