Cacalia tangutica belonged to the tribe Compositae have long been used as Chinese traditional folk herbs to treat headache, dizziness, hemiplegia, rheumatism, tussis and phlegm. Resently, our continuing studies on this plant revealed the presence of diversiform sesquiterpenes from a petrol extract of the aerial parts. The seven sesquiterpenes isolated were three eremophilane sesquiterpenes (1-3) including novel one (1), one known guaianetype sesquiterpeoid (4), one alloromadendrane sesquiterpene (5) and two eudesmane sesquiterpenes (6, 7) (Figure 1). Compound 1, a pink gum, +10 (c 1.30, CHCl3), has the molecular formula C15H22O4 (HR-ESIMS: m/z 267.1597 [M+1], calcd. for C15H23O4 267.1591). Its IR and UV spectra showed the presence of a hydroxyl (3323 cm−1) and α,β-unsaturated carbonyl systems a ketone (1660, 1613 cm−1 and λmax 244 nm, 203 nm). Analysis of the H NMR and C NMR (DEPT) spectrum of 1 along with HMQC experiment, the fifteen signals in C NMR and the signals of four methyl groups (δH: 1.17 s, δC: 18.5; δH: 1.27 d, J = 6.6 Hz, δC: 11.8; δH: 1.51 s, δC: 24.4; δH: 1.55 s, δC: 24.7) identified 1 as eremophlane sesquiterpene. The two olefinic signals (δH: 6.06 s, δC: 125.3 (CH); δH: 7.21 s, δC: 150.9 (CH)) combined with HMBC correlations (δH: 6.06 s/δC: 138.7 (C), 42.9 (C), and 30.2 (CH2); δH: 7.21 s/δC: 47.3 (CH), 42.9 (C), 138.7 (C), 165.7 (C), 185.7 (C), and 83.4 (C)) indicated the presence of characteristics of an 8-oneeremophila-6,9-diene derivative. An additional hydroxy and a peroxyl groups were required for the molecular formula C15H22O4. The signals appeared at δH 3.69 (ddd, 1H, J = 11.4, 11.1, 4.2 Hz) and δC 71.1 (CH) suggested the hydroxy group was equatorial stereochemistry at C-3, while the signals at δH 1.51 s, 1.55 s, 8.78 brs (H-peroxyl, D2O exchanged) and δC 24.4 (CH3), 24.7 (CH3), 83.4 (C) suggested the peroxyl group was at C-11. This was supported by the long range coupling of C-3 (71.1, CH) with the methyl proton (1.27 d, J = 6.6 Hz, H-15) and the long range coupling of C-11 (83.4, C) with the methyl protons (1.51 s, H-12; and 1.55 s, H-13) in the HMBC spectrum. In the HH COSY spectrum, H-4 (δ 1.42 d, J = 11.4 Hz) and H-2 (δ 2.27 m) were also correlated with H-3. To allow the assignments of structure 1 rigorously, a simple reductive reaction has been taken place as followed (see Figure 2). Compound 1 has been selectively reduced to compound 1-1 by potassium iodide in the solution of dilute acetic acid. The produce 1-1, a pale yellow oil, has the molecular α [ ]D 20
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