第2項紅果椌木相關化合物之文獻回顧

自1959 年起開始有了關於椌木屬的化學成分分析文獻，由紐西蘭學者 R. C.

Cambie 從 D. spectabile 中分離出(+)-Catechin (B261)¹⁴¹，屬於一種天然抗氧化物。

1976 年由印度學者 N. M. Khanna 從 D. binectariferum 中分離出 tetranortriterpenoid 類化合物¹⁴²。而1983 年由日本學者 Yuji Hayashi 從 D. acutanggulum 與 D. alliaceum 中分離獲得(+)-8-Hydroxycalamenene (B218)¹⁴³，屬於一種sesquiterpene phenol，具有毒魚之作用；同年，美國學者John D. Leary 於 D. lenticellare 中分離獲得生物鹼

144。其後相關椌木屬研究陸續也發現了萜類(包含三萜、雙萜與倍半萜類)、固醇類、

木質酚素類與精油¹⁴⁵等化學成分，而生物鹼與萜類如前言所示具有許多生物活

性。

萜類之化學結構包含三萜類的dammarane、tirucallane 與 limonoid 等骨架；雙萜類的abietane、labdane、prenyleudesmane 與 ent-pimarane 等骨架。

137

有關過去文獻報導關於椌木屬萜類(triterpenoids、diterpenoids、sesquiterpenoids) 與生物鹼(alkaloid)類與其他結構之研究整理如接續之表格所示，其中化合物 B19-B180 為三萜類，化合物 B181-B200 為三萜苷類，化合物 B201-B217 為雙萜類，

化合物 B218-B230 為倍半萜類，化合物 B231-B241 為固醇類，化合物 B242-B260 為生物鹼類，化合物 B261-B266 為黃酮類(flavonoids)，化合物 B267-B270 為其他 結構。

138

表三十四、Triterpenoid type (依年代排列)

Compounds Sources Published year

Dysobinin (B19)¹⁴² Dysoxylum binectariferum 1976

Dysoxylin (B20)¹⁴⁶ D. richii 1987

Dysoxylone (B21)¹⁴⁷ D. richii 1989

Tigloyldysoxylin (B22)¹⁴⁷ D. richii 1989 6α-Acetoxyobacunol acetate (B23)¹⁴⁷ D. richii 1989

Dysorone A (B24)¹⁴⁸ D. roseum 1991

Dysorone B (B25)¹⁴⁸ D. roseum 1991

Dysorone C (B26)¹⁴⁸ D. roseum 1991

Dysorone D (B27)¹⁴⁸ D. roseum 1991

Dysorone E (B28)¹⁴⁸ D. roseum 1991

Ocotillone (B29)¹²⁶ D. richii 1991

Cabraleone (B30)¹²⁶ D. richii 1991

Shoreic acid (B31)¹²⁶ D. richii 1991

Eichlerianic acid (B32)¹²⁶ D. richii 1991 Methylrichenoate (B33)¹²⁶ D. richii 1991

Richenone (B34)¹²⁶ D. richii 1991

Richenol (B35)¹²⁶ D. richii 1991

Richenoic acid (B36)¹²⁶ D. richii 1991

(20S,24S)-Epoxy-4-hydroxy-3,4-seco- dammar-25(26)-en-3-oic acid (B37)¹⁴⁹

D. richii 1992

Eichlerialactone (B38)¹⁴⁹ D. richii 1992

Dymalol (B39)¹⁵⁰ D. malabaricum 1994

E-Masticadienonic acid (B40)¹⁵¹ D. pettigrewianum 1994 Z-Masticadienonic acid (B41)¹⁵¹ D. pettigrewianum 1994 3α-Hydroxy-Z-masticadienonic acid (B42)¹⁵¹ D. pettigrewianum 1994 Dysoxylic acid A (B43)¹⁵¹ D. pettigrewianum 1994 Dysoxylic acid B (B44)¹⁵¹ D. pettigrewianum 1994 Cabraleadiol (B45)¹⁵² D. malabaricum 1996

Dysoxin 1a (B46)¹⁵³ D. muelleri 1996

Dysoxin 1b (B47)¹⁵³ D. muelleri 1996

Dysoxin 2a (B48)¹⁵³ D. muelleri 1996

Dysoxin 2b (B49)¹⁵³ D. muelleri 1996

Dysoxin 3a (B50)¹⁵³ D. muelleri 1996

139

表三十四、Triterpenoid type(續)

Compounds Sources Published year

Dysoxin 3b (B51)¹⁵³ D. muelleri 1996

16β-Hydroxy-dammara-20(22),25-dien-3- one (B52)¹⁵⁴

D. hongkongense 1998

26-Hydroxy-dammara-20,24-dien-3-one (B53)¹⁵⁴ D. hongkongense 1998 Dipterocarpol (B54)¹⁵⁴ D. hongkongense 1998 (23E)-Cycloart-23-ene-3β,25-diol (B55)¹⁵⁴ D. hongkongense 1998 5α,8α-Epidioxyergosta-6,22-dien-3β-ol (B56)¹⁵⁴ D. hongkongense 1998 Dammaradienol (B57)¹⁵⁴ D. hongkongense 1998 Ocotillol-II (B58)¹⁵⁵ D. cauliflorum 1999 Cabralealactone (B59)¹⁵⁵ D. cauliflorum 1999 23(2425)Abeo-20R,24-dihydroxy-

dammaran-3-one (B60)¹⁵⁵

D. cauliflorum 1999

Methylivorensate (B61)¹⁵⁶ D. spectabile 1999

Nymania-3 (B62)¹⁵⁷ D. malabaricum 1999

Dymacrin A (B63)¹⁵⁸ D. macranthum 1999

Dymacrin B (B64)¹⁵⁸ D. macranthum 1999

Dymacrin C (B65)¹⁵⁸ D. macranthum 1999

Dymacrin D (B66)¹⁵⁸ D. macranthum 1999

Dymacrin E (B67)¹⁵⁸ D. macranthum 1999

Dymacrin F (B68)¹⁵⁸ D. macranthum 1999

Dymacrin G (B69)¹⁵⁸ D. macranthum 1999

Dymacrin H (B70)¹⁵⁸ D. macranthum 1999

Dymacrin I (B71)¹⁵⁸ D. macranthum 1999

Dymacrin J (B72)¹⁵⁸ D. macranthum 1999

Dymacrin K (B73)¹⁵⁸ D. macranthum 1999

Dysoxylumin A (B74)¹⁵⁹ D. hainanense 2000 Dysoxylumin B (B75)¹⁵⁹ D. hainanense 2000 Dysoxylumin C (B76)¹⁵⁹ D. hainanense 2000 3β,22S-Dihydroxy-tirucalla-7,24-dien-23- one

(B77)¹⁶⁰

D. hainanense 2000

22,23-Epoxy-tirucalla-7-ene-3β,24,25-triol (B78)¹⁶⁰ D. hainanense 2000

140

表三十四、Triterpenoid type(續)

Compounds Sources Published year

3β,25-Dihydroxy-tirucalla-7,23-diene (B79)¹⁶⁰ D. hainanense 2000 23,26-Dihydroxy-tirucalla-7,24-dien-3-one (B80)¹⁶⁰ D. hainanense 2000 24,25-Epoxy-3β,23-dihydroxy-7-tirucallene (B81)¹⁶⁰ D. hainanense 2000 Tirucalla-7,24-diene-3β,23-diol (B82)¹⁶⁰ D. hainanense 2000

Aglinin A (B83)¹⁶¹ D. hainanense 2001

Dyvariabilin A (B84)¹⁶² D. variabile 2001 Dyvariabilin B (B85)¹⁶² D. variabile 2001 Dyvariabilin C (B86)¹⁶² D. variabile 2001 Dyvariabilin D (B87)¹⁶² D. variabile 2001 Dyvariabilin E (B88)¹⁶² D. variabile 2001 Dyvariabilin F (B89)¹⁶² D. variabile 2001 Dyvariabilin G (B90)¹⁶² D. variabile 2001 Dyvariabilin H (B91)¹⁶² D. variabile 2001

Niloticin (B92)¹⁶² D. variabile 2001

Dihydroniloticin (B93)¹⁶² D. variabile 2001 21R,23R-Epoxy-21α-ethoxy-24S,25-dihydroxyapotiruca

ll-7-en-3-one (B94)¹⁶³

D. malabaricum 2001

24R-Acetoxy-3β,25-dihydroxycycloartane (B95)¹⁶³ D. malabaricum 2001

Lupeone (B96)¹⁶³ D. malabaricum 2001

Lupeol (B97)¹⁶³ D. malabaricum 2001

Cycloart-25-ene-3β,24-diol (B98)¹⁶³ D. malabaricum 2001 24R,25-Dihydroxycycloartan-3-one (B99)¹⁶³ D. malabaricum 2001 3β,24R,25-Trihydroxycycloartane (B100)¹⁶³ D. malabaricum 2001 Dysoxylumic acid A (B101)¹²⁸ D. hainanense 2002 Dysoxylumic acid B (B102)¹²⁸ D. hainanense 2002 Dysoxylumic acid C (B103)¹²⁸ D. hainanense 2002 Dysoxylumic acid D (B104)¹²⁸ D. hainanense 2002 Dysoxylumolide A (B105)¹²⁸ D. hainanense 2002 Dysoxylumolide B (B106)¹²⁸ D. hainanense 2002 Dysoxylumolide C (B107)¹²⁸ D. hainanense 2002

141

表三十四、Triterpenoid type(續)

Compounds Sources Published year

Lenticellatumin (B108)¹⁶⁴ D. lenticellatum 2003 Beddomeilactone (B109)¹⁶⁵ D. beddomei 2004 3-Oxotirucalla-7,24-dien-23-ol (B110)¹⁶⁵ D. beddomei 2004

Melianone (B111)¹⁶⁵ D. beddomei 2004

Melianodiol (B112)¹⁶⁵ D. beddomei 2004

24-epi-Melianodio (B113)l¹⁶⁵ D. beddomei 2004 Dysoxylin A (B114)¹³⁵ D. gaudichaudianum 2007 Dysoxylin B (B115)¹³⁵ D. gaudichaudianum 2007 Dysoxylin C (B116)¹³⁵ D. gaudichaudianum 2007 Dysoxylin D (B117)¹³⁵ D. gaudichaudianum 2007 Dysoxyhainanin A (B118)¹⁶⁶ D. hainanense 2008 Dysoxyhainanin B (B119)¹⁶⁶ D. hainanense 2008 Acutaxyline A (B120)¹⁶⁷ D. acutangulum 2009 Acutaxyline B (B121)¹⁶⁷ D. acutangulum 2009 Dysoxyhainic acid A (B122)¹⁶⁸ D. hainanense 2009 Dysoxyhainic acid B (B123)¹⁶⁸ D. hainanense 2009 Dysoxyhainic acid C (B124)¹⁶⁸ D. hainanense 2009 Dysoxyhainic acid D (B125)¹⁶⁸ D. hainanense 2009 Dysoxyhainic acid E (B126)¹⁶⁸ D. hainanense 2009 Dysoxyhainol (B127)¹⁶⁸ D. hainanense 2009 Gaudichaudysolin A (B128) ¹⁶⁹ D. gaudichaudianum 2010 Laxiracemosin A (B129)¹²⁹ D. laxiracemosum 2010 Laxiracemosin B (B130)¹²⁹ D. laxiracemosum 2010 Laxiracemosin C (B131)¹²⁹ D. laxiracemosum 2010 Laxiracemosin D (B132)¹²⁹ D. laxiracemosum 2010 Laxiracemosin E (B133)¹²⁹ D. laxiracemosum 2010 Laxiracemosin F (B134)¹²⁹ D. laxiracemosum 2010 Laxiracemosin G (B135)¹²⁹ D. laxiracemosum 2010 Laxiracemosin H (B136)¹²⁹ D. laxiracemosum 2010 3-Oxo-24,25,26,27-tetranortirucall-7-ene-23(21)-la

ctone (B137)¹²⁹

D. laxiracemosum 2010

3-Hydroxy-24,25,26,27-tetranortirucall-7-ene-23(2 1)-lactone (B138)¹²⁹

D. laxiracemosum 2010

142

表三十四、Triterpenoid type(續)

Compounds Sources Published year

Ent-8(9)-pimarene-20-hydroxy-16-nor- 15-oic acid (B139)¹⁷⁰

D. hainanense 2010

20S,24-Epoxy-25,26,27-trisnor-24-oxo-3,4-seco-dammar-4(28),22-dien-3-oic acid (B140)¹⁷⁰

D. hainanense 2010

Ent-8(9)-pimarene-15,16-diol (B141)¹⁷⁰ D. hainanense 2010 Dysoxyhainic acid F (B142)¹³⁴ D. hainanense 2011 Dysoxyhainic acid G (B143)¹³⁴ D. hainanense 2011 Dysoxyhainic acid H (B144)¹³⁴ D. hainanense 2011 Dysoxyhainic acid I (B145)¹³⁴ D. hainanense 2011 Dysoxyhainic acid J (B146)¹³⁴ D. hainanense 2011 Koetjapic acid (B147)¹³⁴ D. hainanense 2011 Dysolenticin A (B148)¹⁷¹ D. lenticellatum 2011 Dysolenticin B (B149)¹⁷¹ D. lenticellatum 2011 Dysolenticin C (B150)¹⁷¹ D. lenticellatum 2011 Dysolenticin D (B151)¹⁷¹ D. lenticellatum 2011 Dysolenticin E (B152)¹⁷¹ D. lenticellatum 2011 Dysolenticin F (B153)¹⁷¹ D. lenticellatum 2011 Dysolenticin G (B154)¹⁷¹ D. lenticellatum 2011 Dysolenticin H (B155)¹⁷¹ D. lenticellatum 2011 Dysolenticin I (B156)¹⁷¹ D. lenticellatum 2011 Dysolenticin J (B157)¹⁷¹ D. lenticellatum 2011 Cumingianol A (B158)¹³⁶ D. cumingianum 2011 Cumingianol B (B159)¹³⁶ D. cumingianum 2011 Cumingianol C (B160)¹³⁶ D. cumingianum 2011 Cumingianol D (B161)¹³⁶ D. cumingianum 2011 Cumingianol E (B162)¹³⁶ D. cumingianum 2011 Cumingianol F (B163)¹³⁶ D. cumingianum 2011 3β-Hydroxytirucalla-7,24-diene-6,23- dione

(B164)¹⁷²

D. lukii 2011

3β-Hydroxytirucalla-7,24-dien-23-one (B165)¹⁷² D. lukii 2011 3β,26-Dihydroxytirucalla-7,24-diene- 6,23-dione

(B166)¹⁷²

D. lukii 2011

143

表三十四、Triterpenoid type(續)

Compounds Sources Published year

(23Z)-3β,26-Dihydroxytirucalla-7,23- diene (B167)¹⁷²

D. lukii 2011

Methyl 6-oxomasticadienolate (B168)¹⁷² D. lukii 2011 3β,16β,21α,25-Tetrahydroxy-20,24-

cyclotirucalla-7(8)-ene (B169)¹⁷²

D. lukii 2011

Dysoxylumstatin A (B170)¹⁷² D. lukii 2011 Dysoxylumstatin B (B171)¹⁷² D. lukii 2011 Dysoxylumstatin C (B172)¹⁷² D. lukii 2011 16β,21α,25-Trihydroxy-20,24-cyclo-

tirucalla-7(8)-en-3-one (B173)¹⁷²

D. lukii 2011

Dubione B (B174)¹⁷² D. lukii 2011

Meliatoosenin B (B175)¹⁷² D. lukii 2011 Dysoxylentin A (B176)¹⁷³ D. lenticellatum 2012 12β-O-Acetyl-15α,28-dihydoxy-17β-

methoxy-3-oxo-20,21,22-23,24,25,26,27-octanor dammanran (B177)¹⁷⁴

D. hainanense 2012

12β-O-Acetyl-15α,17β,28-trihydoxy-3- oxo-20,21,22-23,24,25,26,27-octa- nordammanran (B178)¹⁷⁴

D. hainanense 2012

12β-O-Acetyl-15α,28-dihydoxy-3-oxo- 17-en-20,21,22-23,24,25,26,27-octa- nordammanran (B179)¹⁷⁴

D. hainanense 2012

12β,15α,17β,28-Tetrahydoxy-3-oxo-20, 21,22-23,24,25,26,27-octanordammanran (B180)¹⁷⁴

D. hainanense 2012

144

表三十五、Triterpene glycoside type

Compounds Sources Published year

Cumindysoside A (B181)¹⁷⁵ D. cumingianum 1992 Cumindysoside B (B182)¹³³ D. cumingianum 1992 Cumingianoside A (B183)¹³³ D. cumingianum 1992 Cumingianoside B (B184)¹³³ D. cumingianum 1992 Cumingianoside C (B185)¹³³ D. cumingianum 1992 Cumingianoside D (B186)¹³³ D. cumingianum 1992 Cumingianoside E (B187)¹³³ D. cumingianum 1992 Cumingianoside F (B188)¹³³ D. cumingianum 1992 Cumingianoside G (B189)¹⁷⁶ D. cumingianum 1997 Cumingianoside H (B190)¹⁷⁶ D. cumingianum 1997 Cumingianoside I (B191)¹⁷⁶ D. cumingianum 1997 Cumingianoside J (B192)¹⁷⁶ D. cumingianum 1997 Cumingianoside K (B193)¹⁷⁶ D. cumingianum 1997 Cumingianoside L (B194)¹⁷⁶ D. cumingianum 1997 Cumingianoside M (B195)¹⁷⁶ D. cumingianum 1997 Cumingianoside N (B196)¹⁷⁶ D. cumingianum 1997 Cumingianoside O (B197)¹⁷⁶ D. cumingianum 1997 Cumingianoside P (B198)¹⁷⁷ D. cumingianum 1997 Cumingianoside Q (B199)¹⁷⁷ D. cumingianum 1997 Cumingianoside R (B200)¹³⁶ D. cumingianum 2011

145

表三十六、Diterpenoid type

Compounds Sources Published year

Phyllocladene (B201)¹⁷⁸ D. lenticellare 1986 8β-Hydroxysandaracopimarene (B202)¹⁷⁸ D. lenticellare 1986 Ferruginol (B203)¹⁷⁹ D. lenticellare 1985 Ferrubietolide (B204)¹⁷⁹ D. lenticellare 1985 8β-Methoxysandaracopimarene (B205)¹⁸⁰ D. lenticellare 1988 Dysokusone A (B206)¹⁸¹ D. kuskusense 1998 Dysokusone B (B207)¹⁸¹ D. kuskusense 1998 Dysokusone C (B208)¹⁸¹ D. kuskusense 1998 Isopimara-8(14),15-diene (B209)¹⁵⁶ D. spectabile 1999 7α-Hydroxyisopimara-8(14),15-diene

(B210)¹⁵⁶

D. spectabile 1999

Dysokusone D (B211)¹³² D. kuskusense 2000 Dysokusone E (B212)¹³² D. kuskusense 2000 ent-18-Acetoxy-8(14)-pimarene-15S, 16-diol

(B213)¹⁸²

D. hainanense 2001

ent-18-Acetoxy-16-hydroxy-8(14)- pimarene-15-one (B214)¹⁸²

D. hainanense 2001

ent-16,18-Dihydroxy-8(14)-pimarene-15-one (B215)¹⁸²

D. hainanense 2001

ent-19-Nor-4,16,18-tihydroxy-8(14)- pimarene-15-one (B216)¹⁸²

D. hainanense 2001

Dysoxylumin F (B217)¹⁶⁴ D. lenticellatum 2003

146

表三十七、Sesquiterpenoid type

Compounds Sources Published year

(+)-8-Hydroxycalamenene (B218)¹⁴³ D. acutangulum 1983 (2S,3R)-2,3-Dimethyl-3-(4-methyl-3-

pentenyl)-2-norbornanol (B219)¹⁸³

D. spectabile 1994

Schiffnerone A (B220)¹³⁷ D. schiffneri 1998 Schiffnerone B (B221)¹³⁷ D. schiffneri 1998 Pterocarpol (B222)¹⁶¹ D. hainanense 2001 1-(1-Hydroxy-2-methylpropyl)-

3α-methyl-7-methyleneoctahydroinden- 4-ol (B223)¹⁶²

D. variabile 2001

(+)-Aphanamol I (B224)¹⁶² D. variabile 2001 Dysodensiol A (B225)¹³⁸ D. densiflorum 2008 Dysodensiol B (B226)¹³⁸ D. densiflorum 2008 Dysodensiol C (B227)¹³⁸ D. densiflorum 2008 Dysodensiol D (B228)¹³⁸ D. densiflorum 2008 Dysodensiol E (B229)¹³⁸ D. densiflorum 2008 Dysodensiol F (B230)¹³⁸ D. densiflorum 2008

表三十八、Sterol type

Compounds Sources Published year

β-Sitosterol (B231)¹⁴¹ D. Spectabile 1959 Ergosta-5,24(24')-diene-3β,7α-diol (B232)¹⁸⁴ D. malabaricum 1997 Ergosta-5,24(24')-diene-3β, 4β, 20S-triol

(B233)¹⁸⁴

D. malabaricum 1997

(24R)-Cycloartane-3β-24,25-triol (B234)¹⁸⁴ D. malabaricum 1997 Stigmast-5-ene-3β,7α-diol (B235)¹⁶¹ D. hainanense 2001 Sitoindoside I (B236)¹⁶¹ D. hainanense 2001 Dyscusin A (B237)¹⁸⁵ D. cumingianum 2011 Dyscusin B (B238)¹⁸⁵ D. cumingianum 2011 Dyscusin C (B239)¹⁸⁵ D. cumingianum 2011 24-Ethylcholest-5-en-3β,4β,22-triol (B240)¹⁸⁵ D. cumingianum 2011 Meliavosin (B241)¹⁸⁵ D. cumingianum 2011

147

表三十九、Alkaloid type

Compounds Sources Published year

Dysoxyline (B242)¹⁴⁴ D. lenticellare 1983 S-(+)-Homolaudanosine (B243)¹⁴⁴ D. lenticellare 1983 3-epi-Schelhammericine (B244)¹⁴⁴ D. lenticellare 1983 2,7-Dihydrohomoerysotrine (B245)¹⁴⁴ D. lenticellare 1983 Dysazecine (B246)¹⁴⁴ D. lenticellare 1983 18-Methoxy-2,7-dihydrohomoeryso- trine

(B247)¹⁷⁸

D. lenticellare 1986

3-epi-18-Methoxyschelhammericine (B248)¹³⁰

D. lenticellare 1987

3-epi-12-Hydroxyschelhammericine (B249)¹³⁰

D. lenticellare 1987

Rohitukine (B250)¹⁸⁶ D. binectariferum 1988 Lenticellarine (B251)¹⁸⁷ D. lenticellare 1988 3-epi-2,18-Dimethoxyschel- hammericine

(B252)¹⁸⁰

D. lenticellare 1988

2-α-Methoxycomosivine (B253)¹⁸⁸ D. lenticellare 1994 2-α-Methoxylenticellarine (B254)¹⁸⁸ D. lenticellare 1994 2-α-Hydroxylenticellarine (B255)¹⁸⁸ D. lenticellare 1994 Rohitukine N-oxide (B256)¹⁸⁹ D. binectariferum 2004 Chrotacumine A (B257)¹⁹⁰ D. acutangulum 2009 Chrotacumine B (B258)¹⁹⁰ D. acutangulum 2009 Chrotacumine C (B259)¹⁹⁰ D. acutangulum 2009 Chrotacumine D (B260)¹⁹⁰ D. acutangulum 2009

表四十、Flavone type

Compounds Sources Published year

(+)-Catechin (B261)¹⁴¹ D. Spectabile 1959 Robustaflavone 4',7"-dimethyl ether (B262)¹⁹¹ D. lenticellare 1996 Isoginkgetin (B263)¹⁹¹ D. lenticellare 1996 Bilobetin (B264)¹⁹¹ D. lenticellare 1996 (+)-Evofolin B (B265)¹⁶¹ D. hainanense 2001

Eugenin (B266)¹⁹² D. macrocarpum 2010

148

表四十一、Other type

Compounds Sources Published year

p-Hydroxyacetophenone (B267)¹³⁰ D. lenticellare 1987

Dysoxysulfone (B268)¹³⁹ D. richii 1989

Methyl 3,4-dihydroxybenzoate (B269)¹⁶¹ D. hainanense 2001 Scopoletin (B270)¹⁶¹ D. hainanense 2001

149 Dysobinin (B19) Dysoxylin (B20) Dysoxylone (B21) Tigloyldysoxylin (B22)

6α-Acetoxyobacunol acetate (B23)

Dysorone A (B24) Dysorone B (B25) Dysorone C (B26)

Dysorone D (B27) Dysorone E (B28) Ocotillone (B29) Cabraleone (B30)

Shoreic acid (B31) Eichlerianic acid (B32) Methylrichenoate (B33) Richenone (B34)

150

Richenol (B35) Richenoic acid (B36) (20S,24S)-Epoxy-4-hydroxy-3,4-seco- dammar-25(26)-en-3-oic acid (B37)

Eichlerialactone (B38)

Dymalol (B39) E-Masticadienonic acid (B40) Z-Masticadienonic acid (B41) 3α-Hydroxy-Z-masticadienonic acid (B42)

Dysoxylic acid A (B43) Dysoxylic acid B (B44) Cabraleadiol (B45) Dysoxin 1a (B46)

Dysoxin 1b (B47) Dysoxin 2a (B48) Dysoxin 2b (B49) Dysoxin 3a (B50)

151 Dysoxin 3b (B51)

16β-Hydroxy-dammara-20(22),25-dien-3- one (B52)

Dammaradienol (B57) Ocotillol-II (B58)

Cabralealactone (B59)

23(2425)Abeo-20R,24-dihydroxydammaran-3-one (B60) Methylivorensate (B61) Nymania-3 (B62)

Dymacrin A (B63) Dymacrin B (B64) Dymacrin C (B65) Dymacrin D (B66)

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Dymacrin E (B67) Dymacrin F (B68) Dymacrin G (B69) Dymacrin H (B70)

Dymacrin I (B71) Dymacrin J (B72) Dymacrin K (B73)

Dysoxylumin A (B74)

Dysoxylumin B (B75) Dysoxylumin C (B76) 3β,22S-Dihydroxy-tirucalla-7,24-dien-23-one (B77)

22,23-Epoxy-tirucalla-7-ene-3β,24,25-triol (B78)

3β,25-Dihydroxy-tirucalla-7,23-diene (B79)

23,26-Dihydroxy-tirucalla-7,24-dien-3-one (B80)

24,25-Epoxy-3β,23-dihydroxy-7-tirucallene (B81)

Tirucalla-7,24-diene-3β,23-diol (B82)

153 Aglinin A (B83) Dyvariabilin A (B84) Dyvariabilin B (B85) Dyvariabilin C (B86)

Dyvariabilin D (B87) Dyvariabilin E (B88) Dyvariabilin F (B89) Dyvariabilin G (B90)

Dyvariabilin H (B91) Niloticin (B92) Dihydroniloticin (B93) 21R,23R-Epoxy-21α-ethoxy-24S,25-dihydroxyapotirucall-7-en-3-one (B94)

24R-Acetoxy-3β,25-dihydroxycycloartane (B95) Lupeone (B96) Lupeol (B97) Cycloart-25-ene-3β,24-diol (B98)

154

cycloartan-3-one (B99) 3β,24R,25-Trihydroxy

cycloartane (B100) Dysoxylumic acid A (B101) Dysoxylumic acid B (B102)

Dysoxylumic acid C (B103) Dysoxylumic acid D (B104) Dysoxylumolide A (B105) Dysoxylumolide B (B106)

Dysoxylumolide C (B107) Lenticellatumin (B108) Beddomeilactone (B109) Melianone (B111)

Dysoxylin A (B114) Dysoxylin B (B115) Dysoxylin C (B116) Dysoxylin D (B117)

155

Dysoxyhainanin A (B118) Dysoxyhainanin B (B119) Acutaxyline A (B120) Acutaxyline B (B121)

Dysoxyhainic acid A (B122) Dysoxyhainic acid B (B123)

Laxiracemosin A (B129) Dysoxyhainic acid D (B125)

Dysoxyhainic acid E (B126) Dysoxyhainol (B127) Gaudichaudysolin A (B128)

Laxiracemosin B (B130) Laxiracemosin C (B131) Laxiracemosin D (B132) Laxiracemosin E (B133) Dysoxyhainic acid C (B124)

156 Laxiracemosin F (B134) Laxiracemosin G (B135) Laxiracemosin H (B136)

3-Oxo-24,25,26,27- tetranortirucall-7-ene-23(21)-lactone (B137)

3-Hydroxy-24,25,26,27- tetranortirucall-7-ene-23(21)-lactone (B138)

Dysoxyhainic acid F (B142) Dysoxyhainic acid G (B143) Dysoxyhainic acid H (B144)

Dysoxyhainic acid I (B145) Dysoxyhainic acid J (B146) Koetjapic acid (B147) Dysolenticin A (B148)

Dysolenticin B (B149) Dysolenticin C (B150) Dysolenticin D (B151) Dysolenticin E (B152)

157

Dysolenticin F (B153) Dysolenticin G (B154) Dysolenticin H (B155) Dysolenticin I (B156)

Dysolenticin J (B157) Cumingianol A (B158) Cumingianol B (B159) Cumingianol C (B160)

Cumingianol D (B161) Cumingianol E (B162) Cumingianol F (B163) 3β-Hydroxytirucalla-7,24-diene-6,23- dione (B164)

158

Dysoxylumstatin A (B170) Dysoxylumstatin B (B171) Dysoxylumstatin C (B172)

16β,21α,25-Trihydroxy- 20,24-cyclotirucalla-7(8)-en-3-one (B173)

Dubione B (B174) Meliatoosenin B (B175) Dysoxylentin A (B176)

Cumindysoside A (B181) Cumindysoside B (B182) Cumingianoside A (B183) Cumingianoside B (B184)

159 Cumingianoside C (B185) Cumingianoside D (B186) Cumingianoside E (B187) Cumingianoside F (B188)

Cumingianoside G (B189) Cumingianoside H (B190) Cumingianoside I (B191) Cumingianoside J (B192)

Cumingianoside K (B193) Cumingianoside L (B194) Cumingianoside M (B195) Cumingianoside N (B196)

Cumingianoside O (B197) Cumingianoside P (B198) Cumingianoside Q (B199) Cumingianoside R (B200)

160 Phyllocladene (B201)

8β-Hydroxysandara-copimarene (B202) Ferruginol (B203) Ferrubietolide (B204)

8β-Methoxysandara-copimarene (B205) Dysokusone A (B206) Dysokusone B (B207) Dysokusone C (B208)

Isopimara-8(14), 15-diene (B209)

7α-Hydroxyisopimara-8(14),15-diene (B210) Dysokusone D (B211) Dysokusone E (B212)

Dysoxylumin F (B217) (+)-8-Hydroxycalamenene (B218) (2S,3R)-2,3-dimethyl-3-(4-methyl-3-pentenyl)-2 -norbornanol (B219)

Schiffnerone A (B220)

161

Schiffnerone B (B221) Pterocarpol (B222) (+)-Aphanamol I (B224) Dysodensiol A (B225) Dysodensiol B (B226)

Dysodensiol C (B227) Dysodensiol D (B228) Dysodensiol E (B229) Dysodensiol F (B230)

β-Sitosterol (B231) Ergosta-5,24(24')-diene-3β,7α-diol (B232)

Ergosta-5,24(24')-diene-3β, 4β, 20S-triol (B233)

(24R)-Cycloartane-3β-24,25-triol (B234)

Stigmast-5-ene-3β,7α-diol (B235) Sitoindoside I (B236) Dyscusin A (B237) Dyscusin B (B238)

Dyscusin C (B239)

24-Ethylcholest-5-en-3β,4β,22-triol (B240) Meliavosin (B241)

162

Dysoxyline (B242) S-(+)-Homolaudanosine (B243) 3-epi-Schelhammericine (B244) 2,7-Dihydrohomo-erysotrine (B245)

Dysazecine (B246) 18-Methoxy-2,7-dihydrohomo-erysotrine (B247)

3-epi-18-Methoxy-schelhammericine (B248) 3-epi-12-Hydroxy-schelhammericine (B249)

Rohitukine (B250) Lenticellarine (B251)

3-epi-2,18-Dimethoxy-schelhammericine (B252) 2-α-Methoxycomosivine (B253)

2-α-Methoxylenticellarine (B254) 2-α-Hydroxyl-enticellarine (B255) Rohitukine N-oxide (B256) Chrotacumine A (B257)

Chrotacumine B (B258) Chrotacumine C (B259) Chrotacumine D (B260)

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(+)-Catechin (B261) Robustaflavone 4',7"-dimethyl ether (B262) Isoginkgetin (B263)

Bilobetin (B264) (+)-Evofolin B (B265) Eugenin (B266)

p-Hydroxyacetophenone (B267) Dysoxysulfone (B268) Methyl 3,4-dihydroxybenzoate (B269) Scopoletin (B270)

164

第2節材料與方法

第1項材料介紹

椌木屬(Dysoxylum)，喬木或小喬木，基數或偶數羽狀複葉，葉面無透明之線或腺點；花成錐狀，雙生或單生，花萼具四至五瓣，呈齒狀或近全緣、覆瓦狀；

花瓣具三至六瓣，與雄蕊管上半部或下半部閉合或為分離狀態，呈鑷合狀或覆瓦狀。而雄蕊管口部呈圓柱、全緣、鋸齒狀或頓齒狀；花藥短，與附屬物相間插入雄蕊管喉部，隱沒或半外露；花盤口部呈分離狀，或長或短管狀、頓齒狀或全緣；

子房通常呈二至五室；每室含一至二個胚珠，蒴果呈球形或梨形，革質，具二至五個瓣裂，室背開裂；種子呈假種皮狀或無、無胚乳；子葉疊生或併生，胚根朝

上，近軸，藏於子葉內。目前約有70 種，分布於馬來西亞、澳洲、紐西蘭與臺灣。

而位於臺灣之椌木屬共有四種，分別為蘭嶼樫木(D. arborescens)、蘭嶼椌木(D.

cumingianum)、紅果椌木(D. hongkongense)、大花椌木(D. parasiticum)

¹⁹³。

本次研究之紅果椌木(Dysoxylum hongkongense)，俗稱大葉楝樹、高士佛堅木、

紅果堅木，生長習性為喬木，其葉形態呈小葉三至四對，倒卵狀長橢圓形或卵狀

長橢圓形，先端銳尖至鈍，葉背無毛，小葉柄長約 10 mm；花呈圓錐花序，果實

之稜不明顯，生長環境於臺灣南部與恆春半島低海拔森林中¹⁹⁴。

165

紅果椌木分類地位如下：

Kingdom Plantae 植物界

Phylum Magnoliophyta 木蘭植物門 Class Magnoliopsida 木蘭綱 Order Sapindales 無患子目 Family Meliaceae 楝科 Genus Dysoxylum 椌木屬

Species hongkongense 紅果椌木

第2項分離流程

2010 年七月期間採集獲得之紅果椌木(D. hongkongense)，其枝葉乾重 2.7 公斤，

經由酒精浸泡萃取三次並減壓濃縮後，得到粗萃物 210 公克，再將粗萃物以乙酸

乙酯與水以1:1 的比例進行液液分配萃取三次，獲得乙酸乙酯層與水層，乙酸乙酯

層經減壓濃縮後獲得約146 公克。其中乙酸乙酯層再以正己烷與 75 %甲醇進行第

二次液液分配萃取，獲得甲醇層 86 公克與正己烷層 60 公克。而甲醇層接著利用

快速管柱層析法，以粒徑小於0.063 公釐之矽膠填充管柱，並以正己烷、乙酸乙酯

與甲醇進行梯度沖提，先從100 %正己烷逐漸提高極性至 100 %乙酸乙酯，再以 100

%甲醇沖提管柱，並以薄層色層分析法(TLC)檢測合併相同的極性片段，共獲得 DA1-DA14 共十四個分離片段。初步利用核磁共振光譜分析後，針對片段 DA4 (26.5 g)、DA5 (6.2 g)、DA6 (7.4 g)、DA9 (2.4 g)、DA11 (6.7 g)做進一步的分離純化。

D4 片段取 300 mg 利用 HPLC 以正己烷與乙酸乙酯 85:15 進行沖提，得到新化 合物 B1 (98.4 mg)，獲得之不純物再利用 HPLC 以二氯甲烷與乙酸乙酯 80:20 進行 沖提，得到新化合物 B6 (6.5 mg)與化合物 B17 3-Keto sclareolide (30.9 mg)。

166

D6 (7.4 g)片段利用矽膠管柱層析法，以正己烷與乙酸乙酯 95:5 進行等度沖提，

最後再以100 %甲醇沖提，經 TLC 檢測後得到分離片段 DA6-3。DA6-3(61 mg)再

利用矽膠管柱層析法，以正己烷與丙酮97:3 進行等度沖提，最後再以 100 %甲醇

沖提，經TLC 檢測後得到分離片段 DA6-3-3。DA6-3-3 (33 mg)利用 HPLC 以正己烷與乙酸乙酯80:20 進行沖提，得到新化合物 B3 (14.7 mg)。

D9 (2.4 g)片段利用矽膠管柱層析法，以正己烷與乙酸乙酯 60:40 進行等度沖提，

最後再以100 %甲醇沖提，經 TLC 檢測後得到分離片段 DA9-8。DA9-8 (311 mg)

再利用矽膠管柱層析法，以正己烷與丙酮80:20 進行等度沖提，最後再以 100 %甲

醇沖提，經TLC 檢測後得到分離片段 DA9-8-4。DA9-8-4 (38 mg)利用 HPLC 以正己烷與乙酸乙酯80:20 進行沖提，得到化合物 B18 Isoscopoletin (2.4 mg)。

D11 (6.7 g)片段利用矽膠管柱層析法，以正己烷與乙酸乙酯 60:40 進行等度沖提，最後再以 100 %甲醇沖提，其中含有析出之結晶為化合物 B16 2β,3β,4β-Tri- hydroxypregnan-16-one (32.6 mg)，經 TLC 檢測後得到分離片段 DA11-10。DA11-10 (201 mg)再利用矽膠管柱層析法，以正己烷與丙酮 80:20 進行等度沖提，最後再以 100 %甲醇沖提，經 TLC 檢測後得到分離片段 DA11-10-3。DA11-10-3 (69 mg)利用 HPLC 以正己烷與乙酸乙酯 30:70 進行沖提，得到新化合物 B2 (13.6 mg)。

D5 (6.2 g)片段利用矽膠管柱層析法，以正己烷與乙酸乙酯 85:15 進行等度沖提，

最後再以100 %甲醇沖提，經 TLC 檢測後得到分離片段 DA5-8。DA5-8 (1.58 g)再

利用矽膠管柱層析法，以正己烷與丙酮80:20 進行等度沖提，最後再以 100 %甲醇

沖提，經TLC 檢測後得到分離片段 DA5-8-2 與 DA5-8-3。DA5-8-2 (1066 mg)利用 HPLC 以正己烷與乙酸乙酯 65:35 進行沖提，獲得片段 DA5-8-2-3~8 仍皆為不純物。

DA5-8-2-3 再利用 HPLC 以二氯甲烷與乙酸乙酯 85:15 進行沖提，得到新化合物 B12 (4.4 mg)與新化合物 B13 (5.1 mg)。DA5-8-2-4 再利用 HPLC 以二氯甲烷與乙酸

乙酯85:15 進行沖提，獲得之不純物再以正己烷與丙酮 75:25 進行沖提，得到新化

167

合物 B11 (16.6 mg)。DA5-8-2-5 再利用 HPLC 以二氯甲烷與乙酸乙酯 87:13 進行沖 提，得到首次從天然物分離之化合物 B15 cis-5α-Pregn-17(20)-en-3,16-dion (7.6 mg)，

剩下之不純物再以甲醇與水 80:20 進行沖提，得到新化合物 B14 (77.1 mg)。

DA5-8-2-6 再利用 HPLC 以二氯甲烷與乙酸乙酯 85:15 進行沖提，得到新化合物 B9 (110.1 mg)。DA5-8-2-8 再利用 HPLC 以二氯甲烷與乙酸乙酯 80:20 進行沖提，

獲得片段DA5-8-2-8-4 與 DA5-8-2-8-8 仍皆為不純物。DA5-8-2-8-4 再以正己烷與丙酮 85:15 進行沖提，得到新化合物 B7 (5.1 mg)與新化合物 B8 (33.1 mg)。

DA5-8-2-8-8 再以正己烷與丙酮 85:15 進行沖提，得到新化合物 B4 (7.0 mg)與新化 合物 B5 (9.7 mg)。DA5-8-3 (312 mg)利用 HPLC 以正己烷與乙酸乙酯 55:45 進行沖 提，得到新化合物 B10 (14.2 mg)。

以下為紅果椌木(D. hongkongense)枝葉之分離流程圖 I~IV

在文檔中華中五味子果實與紅果椌木枝葉之活性成分研究 (頁 166-200)

第2項 紅果椌木相關化合物之文獻回顧

第2節 材料與方法

第1項 材料介紹

cumingianum)、紅果椌木(D. hongkongense)、大花椌木(D. parasiticum)

第2項 分離流程

第2節材料與方法

第1項材料介紹

第2項分離流程