Comanthus parvicirrus (小卷海齒花 )

動物界 (Animalia)棘皮動物門 (Echinodermata)海百合綱 (Crinoidea)關節亞鋼 (Articulata)海羊齒目 (Comatulida)櫛羽星科 (Comasteridae)

為一種始見於石炭紀的棘皮動物，生活於海裡，具多條腕足，身體呈花狀，錶面有石灰質的殼。常棲息於岩縫、石、軟珊瑚的基部。

抽取與分離

General Experimental Procedures.

UV spectra were measured in MeOH on a Perkin-Elmer Lambda 15 UV/vis spectrometer.

IR spectra were recorded on an ATI Mattson Genesis FTIR, using KBr discs.

1H, 13C, and all other NMR 2D experiments were recorded in CDCl3, either on a Varian Unity INOVA 400 MHz spectrometer or on a Bruker Avance 600 MHz spectrometer with a cryoprobe.

TMS was used as an internal reference for the 1H NMR spectra, and the CDCl3 signal at 77.0 ppm was used as a reference for 13C NMR spectra.

ESIMS was carried out on a Perseptive Biosystem Mariner LC-MS. HRESIMS analysis was carried out at the EPSRC National Mass Sp

ectrometry Service Centre in Swansea (UK). HPLC separations were carried out using a Phenomenex reversed-

phase (C18, 10 × 250 mm, 5 μm) HPLC column and an HP1100 HPLC system (Agilent Technologies)

with a diode array detector (DAD).

MeOH extract of C. parvicirrus (1.1g dry weight)

Partitioned by H2O-CH2Cl2 fractionation

H2O-soluble CH2Cl2-soluble

50% MeOH-soluble

Compound 1 (61 mg)Compound 2 (34 mg)

Reversed-phase HPLC

抽取與分離

Hexanes/10%MeOH Partitione

Extracted with CH2Cl2

CH2Cl2-soluble

OOCH3

HO

OCH3

OH

O

11

4

4a

66a

10a 10b

OOCH3

HO

OCH3

OCH3

O10b10a

6a6

4a

4

11

naphthopyrones 6-methoxycomaparvin (1)

6-methoxycomaparvin 5-methyl ether (2)

結構解析

naphthopyrones 6-methoxycomaparvin (1)brown needle-shaped crystals

UV (MeOH) λmax (logε) 245 (4.57), 290 (4.37), 380 (3.77) nm

IR (KBr) νmax 3341, 2950, 1667, 1615, 1571, 1537, 1448 cm-1

LRESIMS m/z 331 [M + H]+ (C18H18O6)

HRESIMS m/z 331.1176 [M + H]+, (calc for C18H19O6)1H NMR (400 MHz, CDCl3) δ :

OOCH3

HO

OCH3

OH

O

11

4

4a

66a

10a 10b

6.23 (1H, s, H-3)

7.01 (1H, d, J=1.6 Hz, H-7)

6.43 (1H, d, J=1.6 Hz, H-9)

6.23 (2H, t J=7.7 Hz, H-11)

1.8 (2H, m, H-12)

Methine (CH)

Methylene (CH2)1.01 (3H, t, H-13)

3.94 (3H, s, H-16)

3.95 (3H, s, H-15)

Methyl (CH3)

12.90 (s, OH-5)

13C NMR :

OOCH3

HO

OCH3

OH

O

11

4

4a

66a

10a 10b

170.1 (C-2)

183.4 (C-4)

147.1 (C-4a)

109.3 (C-5)

134.7 (C-6)

158.3 (C-6a)

104.9 (C-8)

160.2 (C-10)136.1 (C-10a) 152.4 (C-10b)

109.5 (C-3)

96.3 (C-7)

96.7 (C-9)

36.5 (C-11)

20.0 (C-12)

13.7 (C-13)

60.4 (C-15)

56.2 (C-16)

HMBC

OOCH3

O

OCH3

O

O

H

H

H

H

H

H

HH

11

4

4a

66a

10a 10b

COSY

OOCH3

O

OCH3

O

O

H

H

H

H

H

H

HH

11

4

4a

66a

10a 10b

single-crystal X-ray diffraction analysis

6-methoxycomaparvin 5-methyl ether (2)

brown needle-shaped crystalsUV (MeOH) λmax (logε) 240 (4.58), 280 (4.51), 365 (4.05) nmIR (KBr) νmax 3229, 2960, 1642, 1584, 1415 cm-1LRESIMS m/z 345 [M + H]+ (C19H20O6) HRESIMS m/z 345.1337 [M + H]+, (calc for C19H21O6)1H NMR (400 MHz, CDCl3) δ :

OOCH3

HO

OCH3

OH

O

11

4

4a

66a

10a 10b

OOCH3

HO

OCH3

OCH3

O10b10a

6a6

4a

4

11

naphthopyrones 6-methoxycomaparvin (1)

6-methoxycomaparvin 5-methyl ether (2)

12.90 (s, OH-5)3.93 (s, H-14)

OOCH3

HO

OCH3

OH

O

11

4

4a

66a

10a 10b

OOCH3

HO

OCH3

OCH3

O10b10a

6a6

4a

4

11

naphthopyrones 6-methoxycomaparvin (1)

6-methoxycomaparvin 5-methyl ether (2)

13C NMR :

62.0 (C-14)

HMBC

OOCH3

HO

OCH3

OCH3

O10b10a

6a6

4a

4

11