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 ...
