全 文 ：上新世云南铁杉木化石的化学成分
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赵友兴1 , 李承森2 , 罗晓东1 , 周 露3 , ?铁梅2 , 周 俊1
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(1 中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室 , 云南 昆明 650204;
2 中国科学院植物研究所 , 北京 100093; 3 云南省香料研究开发中心 , 云南 昆明 650051 )
摘要 : 为了研究在褐煤中发现的上新世云南铁杉 (Pliocene Tsuga dumosa) 木化石的化学成分 , 采用气相色谱
- 质谱联用技术和柱层析方法分别检测了 22 个挥发性成分和分离鉴定了 9 个化合物 (1 - 9) , 化学成分类型
包括烷烃 (C16 -C32 )、脂肪酸、甾体、三萜、邻苯二甲酸酯及酚性成分。化合物结构采用波谱方法鉴定。
关键词 : 上新世化石 ; 化学成分 ; 云南铁杉
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2007) 03 - 367 - 04
Palaeophytochemical Constituents from the Pliocene-fossil
Wood of Tsuga dumosa (Pinaceae) *
ZHAO You-Xing1 , LI Cheng-Sen2 , LUO Xiao-Dong1 , ZHOU Lu3 , YI Tie-Mei2 , ZHOU Jun1 * *
(1 State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Instituteof Botany, Chinese Academy
of Sciences, Kunming 650204 , China; 2 Instituteof Botany, ChineseAcademy of Sciences, Beijing 100093 , China;
3 Yunnan Development & Research Center of F & F , Kunming 650051 , China)
Abstract: Palaeophytochemical investigation of the Pliocene-fossil wood of Tsuga dumosa found in brown coal led to the
detection of 22 volatiles and the isolation of 9 compounds (1 - 9) , including six types of n-alkanes (C16 up to C32 ) , fatty
acids, steroids, triterpenoids, phthalatesandaromatic compounds . Their structureswereelucidated onthebasis of spectro-
scopic evidence .
Key words: Pliocene-fossil ; Constituents; Tsuga dumosa
The analysis of chemical constituents in specific
plant fossils provides crucial information for their prob-
able diagenetic pathways and chemical preservation .
Natural products inplant fossils could retain their char-
acteristic basic structural skeletons and be used as che-
mosystematic marker or biomarkers for their biological
origin, though they may undergo rapid diagenetic pro-
cesses and chemical transformations during their fossil-
ization ( Peakman and Maxwell , 1988; Schüpfer and
Gülacar, 2000; Otto et al . 2001 , 2002) . Some natu-
ral flavonoids and other constituents were detected from
Cretaceous, Pliocene, Miocene and Eoceneplants, pre-
viously ( Zhao et al . 2005 a, b , 2006; Giannasi and
Niklas, 1977; Niklas and Giannasi , 1977 , 1978; ) .
Abundant plant and animal fossilsoccured in complicat-
ed strata in west Yunnan Province, China (Ge et al .
1999) , part of which were buried in coal-bearing ba-
sins . Tsuga dumosa is an economically important conifer
indigenous to the Yunnan Province of China (Southwest
College of Forestry, Yunnan Forestry Administration,
1988) . Sesquilignans and lignans fromthis genus have
been reported, previously (Zhao et al . 2004 , 2005c) .
A piece of Pliocene-fossil wood of T. dumosa, which
was preserved morphologically , was discovered in an
云 南 植 物 研 究 2007 , 29 (3) : 367～370
Acta Botanica Yunnanica

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?? ?Author for correspondence; Tel : + 86 871 522 3264; Fax: + 86 871 522 3261 ; E-mail: jzhou@ mail . kib. ac. cn
Received date: 2006 - 11 - 16 , Accepted date: 2007 - 02 - 08
作者简介 : 赵友兴 (1974 - ) 男 , 理学博士 , 主要从事植物化学研究。 ?
Foundation item: supported by the National Natural Science Foundation of China ( No . 40403014 ) and the Knowledge Innovation Program of the
Chinese Academy of Sciences ( KZCX1-10-01 , KZCX2-SW-118) .
Fig . 1 Structures of compounds 1 - 9
open coalmine in Changning of Yunnan Province, Chi-
na, raising questions about its phytochemical constitu-
ents . In this paper, we reported the palaeophytoche-
mical invstigationon the Pliocene-fossil wood of T. du-
mosa by phytochemical methods including gas chroma-
tography-mass spectrometry ( GC-MS ) and column
chromatography to probe their organic constituents .
A methanol extract prepared from the Pliocene-
fossil wood of T. dumosa was chromatographyed repeat-
edly by column chromatography on silicagel and Seph-
adex LH-20 and then subjected to preparativethin-layer
chromatography, yielding nine compounds ( 1 - 9 )
(Fig . 1 ) . Their structures were elucidated as C32 ho-
panoic acid ( 1) ( Taylor et al . 1980) , gammacer-16-
ene-3-one ( 2 ) ( Macias et al . 1996 ) , 24S-ethyl-
chlestan-3α-ol (3 ) ( Zhao et al . 2005a; Yano et al .
1992) , 3β-sitosterol (4) ( Zhao et al . 2005a; Seo et
al . 1992) , stigmastan-3-one (5) (Zhao et al . 2005a;
Gaspar et al . 1993 ) , 4-hydroxy-benzaldehyde ( 6 )
(Magnusson et al . 1963) , 4-hydroxy-3-methoxy-benz-
aldehyde (7) ( Hanke and Kubo, 1989) , bis ( 2-ethyl-
hexyl ) phthalate ( 8) ( Barend, 1980 ) , glycerol 1 , 3-
di -( 9 E-octadecenoate) 2-hexadecanoate ( 9 ) (Minor
and Lutton, 1953 ) according to the analysis of their
spectral data and literature . The spectrumof gas chro-
matography-mass spectrometry (GC-MS) exhibited over
26 peaks, among which 22 constituents were detected
from the ether extract of the Pliocene-fossil wood of
T. dumosa, includingmainly three types of fatty acid,
n-alkanes (C16 up to C32 ) and phthalates ( Table 1) .
The fossilized Pliocene plants may have experi-
enced various physical , biological , and chemical
changes over the long years, resulting in generation of
diagenetic products in fossil material after its burial in
sediment . Phytochemical investigation of the Pliocene-
fossil wood of T. dumosa indicated that the components
Table 1 Volatiles from the Pliocene-fossil wood of T. dumosa
No . Compounds
Retention
time
Molecular
formula
Relative
content ( % ) No . Compounds
Retention
time
Molecular
formula
Relative
content ( % )
1 ?Eucalyptol 6 . 12 C9 ]H18 O 1 l. 21 12 ?Tricosane 34 .05 C23 ?H48 4 . 20
2 ?Vanillin 15 .09 C8 ]H8 O3 0 l. 81 13 ?Tetracosane 35 .82 C24 ?H50 8 . 24
3 ?Hexadecane 19 .27 C16 uH34 0 l. 47 14 ?Pentacosane 37 .62 C25 ?H52 8 . 12
4 ?Heptadecane 21 .67 C17 uH36 0 l. 47 15 ?Bis (2 ;-ethylhexyl) phthalate 38 .84 C24 ?H38 O4 18 .40
5 ?Tetradecanoic acid 23 .32 C14 uH28 O2 0 l. 47 16 ?Hexacosane 39 .64 C26 ?H54 7 . 55
6 ?Octadecane 23 .97 C18 uH38 0 l. 46 17 ?Heptacosane 41 .97 C27 ?H56 7 . 53
7 ?Diisobutyl phthalate 25 .74 C16 uH22 O4 0 l. 63 18 ?Octacosane 44 .74 C28 ?H58 10 .13
8 ?Hexadecanoic acid 27 .74 C16 uH32 O2 6 l. 54 19 ?Nonacosane 48 .10 C29 ?H60 6 . 25
9 ?Heneicosane 30 .27 C21 uH44 0 l. 79 20 ?Triacontane 52 .22 C30 ?H62 3 . 81
10 ?Octadecanoic acid 31 .67 C18 uH36 O2 6 l. 75 21 Hentriacontane 57 .30 C31 ?H64 2 . 65
11 ?Docosane 32 .20 C22 uH46 1 l. 88 22 Dotriacontane 63 .65 C32 ?H66 1 . 68
863 云 南 植 物 研 究 29 卷
identified from fossil T . dumosa were different from
those reported in extant species ( Zhao et al . 2004 ,
2005c) becauseof probable chemical transformations or
transfer of constituentsbetween fossil material and sedi-
ment . Gammaceranes are used as paleo-biomarker
(Macias et al . 1996 ) . Phenolic compounds 6 and 7
may be the degradation products of lignans distributed
in extant T. dumosa (Otto and Simoneit, 2001; Zhao
et al . 2004 , 2005c) . Phthalate ester ( 8 ) , also de-
tected from the volatiles of this fossil plant, was well-
known commercial application to insect repellents (Ba-
rend, 1980 ) . Three steroids (3 - 5) were common ex-
isted in Pilocene fossil Pinus armandii in our previous
research (Zhao et al . 2005a) . The chemical preserva-
tion of the Pliocene-fossil wood of T. dumosa may be
linked to the presence of insect repellants ( such as
phthalates) , anti-oxidants ( phenolic compounds) , and
wax (series of alkanes and fatty acids) during thelong-
term period .
Experimental
General Experimental Procedures MS spectrawere car-
ried out on a VG Auto Spec-3000 spectrometer . The 1D NMR
spectra were obtained on BRUKER AV-400 and DRX-500 spec-
trometers . TLC was carried out on silica gel G precoated plates .
Separation and purification wereperformed by columnchromatog-
raphy on silica gel (200 - 300 mesh) .
Plant Material The Pliocene-fossil wood of Tsuga dumo-
sa was collected from an open coalmine in Changning of Yunnan
Province, People′s Republic of China, and identified by profes-
sor Li Cheng-Sen . A voucher specimen ( LL-1-3 ) has been de-
posited in Institute of Botany, Chinese Academy of Sciences,
People′s Republic of China .
Analysis of volatiles The powdered Pliocene-fossil wood
of T. dumosa (0 . 010 kg) was extractedfor 24 h withmethanol at
room temperature . The extract was concentrated in vacuum at
roomtemperature to givethe residue, which were partitioned be-
tween ether andmethanol (approximately 95% ) togivethe ether
layer and methanol layer, respectively . The ether extracts ( 15
mg) was subjected to GC-MS analysis . The GC was operated as
follows: analysis column, 30QC2?AC5 (30 m×0 .25 mm) ; col-
umn temperature, held from 100℃ and ramped at 5℃?min to
280℃ ; elution, pure He; concentration of ether extract, 4 mg?
mL ; and injection volume, 0 .4μL . The MS was operated in full
scanmode (35 - 450 , 1 scan?s, 70 eV ionizationenergy) . Peaks
were identified by comparison of their relative retention times,
andmass spectral characteristics, with NBS massspectral library
software and relative literatures .
Extraction and Isolation The powdered Pliocene-fossil
woodof T. dumosa (2 . 80 kg) wereextracted withMeOH (8 L×
3) at 60℃ for 4 hr each time and filtered . The residue (27 g)
was subjected to column chromatography on silica gel ( 200 - 300
mesh) , elutedwith gradient chloroform?methanol (12∶1) toyield
5 fractions . Fraction 4 was further separated over Si-gel column
developed with petroleumether?acetone (4∶1) andand over Seph-
adex LH-20 to afford compound 1 (6 mg) , 6 (20 mg) and 7 (38
mg) . Fraction3 waspurified by repeated silicagel columnchrom-
atography eluted with petroleumether?acetone (6∶1 , 5∶1) and pe-
troleumether?chloroform (1∶1) to yield2 (5 mg) , 3 (46 mg) , 4
(40 mg) and5 (15 mg) , respectively . Fraction1 wasfurther sep-
aratedover Si-gel column (petroleum ether?acetone 40∶1 , petro-
leumether?chloroform1∶1) to give 8 (8 mg) and 9 (50 mg) .
C32 hopanoic acid (1 ) C32 H54 O2 , white amorphous pow-
der; mp: 162 - 164℃ ; EI-MS m?z: 470 [M ] + ( 30 ) , 455
(16) , 249 (31) , 191 (100) , 163 (21) , 150 (14) , 135 (15) ,
121 (19) , 109 (25) , 95 ( 47 ) . 1 H NMR (400 MHz, CDCl3 )δ
0 .98 , 0 .92 , 0 .90 , 0 .82 , 0 .80 , 0 .77 (3H each, s, H - 22 ,
23 , 24 , 25 , 26 , 27) , 0. 88 (3H, d, J = 6 .3 Hz, H - 29) ; 13 C
NMR (100 MHz, CDCl3 )δ178 .8 (s, C - 32) , 56 .0 ( d, C -
5) , 50 .6 ( d, C - 9 ) , 48 .3 ( d, C - 17 ) , 46 .4 ( d, C - 13 ) ,
43 .8 (s, C - 8) , 41 .8 (t, C - 3) , 41 .1 ( t, C - 1 ) , 41.0 (s, C
- 14) , 40 .0 (t, C - 31) , 38 .7 (d, C - 21 ) , 37.1 (s, C - 18) ,
35 .7 ( d, C - 28) , 33 .1 ( q, C - 27) , 32 .9 (s, C - 10 ) , 32 .7
(t, C - 19) , 31 .9 (t, C - 30) , 31 .6 (s, C - 4) , 27 .6 ( t, C -
7) , 26.4 (t, C - 15 ) , 25 .4 (t, C - 20 ) , 23 .7 , 17.8 , 16 .4 ,
16 .0 , 15 .8 , 13 .8 (q, C - 22 , 23 , 24 , 25 , 26 , 29) , 23 .3 ( t,
C - 11) , 22.4 ( t, C - 16) , 21 .9 (t, C - 12) , 18 .4 (t, C - 2) ,
18 .3 (t, C - 6) .
Gammacer-16-ene-3-one (2) C30 H48 O, colorless oil ; EI-
MS m?z: 424 [M ] + ( 8 ) , 409 ( 5 ) , 331 ( 15 ) , 218 ( 90 ) ,
203 (50) , 191 ( 36) , 173 ( 24) , 163 ( 26 ) , 149 (40 ) , 137
(42) , 123 ( 55) , 109 ( 68) . 1 H NMR ( 400 MHz, CDCl3 ) δ
5 .19 ( 1H, brs, H - 16 ) , 1 . 23 , 1 .12 , 1 .07 , 1 .05 , 1.04 ,
1 .00 , 0 .85 , 0 .82 (3H each, s, H - 23 , 24 , 25 , 26 , 27 , 28 ,
29 , 30) ; 13 C NMR ( 100 MHz, CDCl3 ) δ 217 .8 ( s, C - 3 ) ,
145 .3 (s, C - 17) , 121 .5 (d, C - 16) , 55 .3 ( d, C - 5) , 47 .5
(s, C - 4) , 47 .3 (d, C - 9) , 46 .9 ( d, C - 13 ) , 46 .8 ( t, C -
21) , 42 .1 (s, C - 8) , 39 .8 (s, C - 14) , 39 .3 ( t, C - 19 ) ,
37 .1 (t, C - 1) , 36 .7 (s, C - 18) , 34.7 (t, C - 2) , 34.2 ( t,
C - 15) , 34 .1 (s, C - 10) , 33 .3 ( q, C - 30) , 32 .5 ( s, C -
22) , 32 .2 (t, C - 7 ) , 28 .4 ( q, C - 29) , 26 .5 ( q, C - 23 ) ,
25 .9 (q, C - 24) , 23 .7 (t, C - 12 ) , 23 .7 (t, C - 11) , 21 .5
( q, C - 28) , 19.7 (t, C - 6 ) , 18 .7 (t, C - 20 ) , 16.7 ( q, C -
27) , 15 .2 ( q, C - 26) , 14 .1 ( q, C - 25) .
24S-Ethyl-chlestan-3α-ol (3 ) C29 H52 O, white needle ( ac-
etone) ; mp: 134 - 136℃ ; EI-MS m?z: 416 [M] + (100) ; 1 H
NMR and 13 C NMR data were consistent with those in the litera-
ture (Zhao et al . 2005a; Yano et al . 1992) .
Stigmastan-3-one (5) C29 H50 O, whiteamorphous powder;
mp: 157 - 159℃ ; EI-MS m?z: 414 [M] + ( 100 ) ; 1 H NMR
and 13 C NMR data were consistent with those in the literature
(Zhao et al . 2005a) .
9633 期 ZHAO You-Xing et al .: Palaeophytochemical Constituents from the Pliocene-fossil Wood . . .
4-Hydroxy-benzaldehyde ( 6 ) C7 H6 O2 , white amorphous
powder; mp: 115 - 116℃ ; EI-MS m?z: 122 [M] + (14) ; 1 H
NMR (400 MHz, CD3 OD)δ9.75 (1H, s, C - ?HO) , 7. 75 (2H,
d, J = 8.5 Hz, H - 2 , 6) , 6 . 89 (2H, d, J = 8 .5 Hz, H - 3 ,
5) ; 13 C NMR (100 MHz, CD3 OD) δ192 .8 (s, - ?CHO) , 165 .1
(d, C - 4 ) , 133 .4 ( d, C - 2 , 6) , 130 .3 (s, H - 1) , 116 .9
(d, C - 3 , 5) .
4-Hydroxy-3-methoxy-benzaldehyde (7) C8 H8 O3 , color-
less needles ( acetone) ; mp: 81 - 82℃ ; EI-MS m?z 152 (M+ ,
40) ; 1 H NMR ( 500 MHz, CDCl3 ) δ 9 .78 ( 1H, s, CHO) ,
7 . 39 (1H, dd, J = 2 .2 , 8 .5 Hz, H - 6) , 7. 38 ( 1H , d, J =
2 .2 Hz, H - 2 ) , 7. 01 ( 1H, d, J = 8 .5 Hz, H - 5) , 3 . 92
(3H, s, OCH3 ) ; 13 C NMR ( 125 MHz, CDCl3 ) δ 190 .9
(CHO) , 151 .8 ( C - 4) , 147.2 (C - 3 ) , 129 .8 (C - 1) , 127 .5
(C - 6) , 114 .4 (C - 5) , 108 .8 ( C - 2) , 56 .1 (OCH3 ) .
Bis (2-ethylhexyl) phthalate (8) C24 H38 O4 , viscous oil;
EI-MS m?z 390 (M+ , 6) , 280 (65) , 149 (100) , 113 ( 72 ) .
1 H NMR ( 400 MHz, CDCl3 ) δ 7.68 ( 2H , dd, J = 3 .4 , 5 .7
Hz, H - 2 ) , 7. 51 ( 2H , dd, J = 3 .4 , 5 .7 Hz, H - 3) , 4 . 19
(4H , d, J = 6 .5 Hz, H - 1′) , 1 . 65 (2H , m, H - 2′) , 1 .23 -
1 .42 (16H, m, H - 3′, 4′, 5′, 7′) , 0 . 90 (6H, t, J = 7 .4
Hz, H - 8′) , 0 . 88 ( 6H , t, J = 7 .8 Hz, H - 6′) ; 13 C NMR
(100 MHz, CDCl3 ) δ167 .8 ( CO) , 132 .4 ( C - 1 ) , 130.9 ( C
- 3) , 128 .8 (C - 2 ) , 68 .1 (C - 1′) , 38 .7 (C - 2′) , 30.3 ( C -
3′) , 28 .9 ( C - 4′) , 23 .7 ( C - 7′) , 23 .0 (C - 5′) , 14 .0 (C -
6′) , 10 .9 ( C - 8′) .
Glycerol 1 , 3-di - (9 E-octadecenoate) 2-hexadecanoate
(9) C55 H102 O6 , viscous oil ; EI-MS m?z: 620 ( [M-C16 H30
O] + , 1 ) ; 1 H NMR ( 400 MHz, CDCl3 ) δ 5 .36 - 5.23 (5H,
m, H - 1 , 2 , 3 ) , 4 . 29 - 4 .09 ( 4H , m, C - ?H = C ?H ) , 0 . 85
(9H, t, J = 6 .4 Hz, C - 脓H3 ) ; 13 C NMR ( 100 MHz, CDCl3 ) δ
173 .2 ( s, 1 , 3-CH2 OO - ?C) , 172 .8 ( s, 2-CHOO ?C) , 130 .0 ,
129 .7 (d, - 苹CH = 苹CH) , 68 .9 ( d, C - 2 ) , 62 .1 ( t, C - 1 , 3 ) ,
34 .2 , 34 .0 , 29.5 , 27 .2 , 24 .8 , 22 .6 [ t, ( CH2 )7 ,
(CH2 )14 ] , 14 .1 ( q, CH3 ) .
Acknowledgements : All spectra were recorded by the analytical
group of the State Key Laboratory of Phytochemistry and Plant
Resources in West China, Kunming Institute of Botany, Chinese
Academy of Sciences .
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073 云 南 植 物 研 究 29 卷