忍冬屬之化學成分考察

依據梁曉天的常用中藥基礎研究⁴¹，將忍冬屬植物的化學成分 分為揮發油（volatile oil）、黃酮（flavonoids）、三萜及三萜皂苷類

（triterpenoids＆triterpenoidal saponin）、iridoid、苯丙素類

（penylpropanoids）、有機酸衍生物（organic acid derivatives）和其 他類（others）等七大類。 Lonicera caerulea L.var. emphyllocalyx N^AKAI.

fresh leaves quercetin (1)

quercetin-3-rhamnoside (2) quercetin-3-O-β-D-glucoside (3) eriodictyol-7-glucoside (4)

42

Lonicera confusa DC.

flower buds rutin (5) quercetin(1)

luteolin-7-O-β-D-galactoside (6)

lonicerin (luteolin 7-O-neohesperidoside) (7) luteolin (8)

tricin-7-O-β-D-glucopyranoside (9) chrysoeirol-7-O-neohesperidoside (10) tricin-7-O-neohesperidoside (11)

43 44

Lonicera gracilipes var. glandulosa M^AXIM.

fresh leaves apigenin -7-O-( 2^G-rhamnosyl )- gentiobioside (12)

cosmosiin

(apigenin 7-O-β-D-glucopyranoside) (13) rhoifolin (14)

(apigenin-7-O-neohesperidoside) apigenin-7-O-gentiobioside (15) apigenin-7-O-sophoroside (16) luteolin-7-O-glucoside (17) luteolin-7-O-neohesperidoside (7) luteolin-7-O-gentiobioside (18)

45

Lonicera implexa A^ITON.

leaves implexaflavone (19)^* madreselvin A (20)^* madreselvin B (21)^* ochnaflavone (22) rhoifolin (14) luteolin (8)

luteolin-7-O-β-D-glucopyranoside (23) apigenin-7-O-primeveroside (24)

46

apigenin-7-O-β-D-glucopyranoside (13) apigenin-7-O-rutinoside (25)

3-methoxyquercetin-7-O-β-D-glucopyranoside (26)

fresh aerial

parts hydnocarpin (27) quercetin (1) ochnaflavone (22)

ochnaflavone-4^’-O-methyl ether (28) astragalin (29)

isoquercetin (30) rhoiflon (14)

47 Lonicera japonica

THUNB.

flower buds luteolin-7-O-D-glucoside (17) luteolin-7-O-β-D-galactoside (6) quercetin-3-O-β-D-glucoside (3) hyperoside (31)

luteolin (8) corymbosin (32)

5-hydroxy-7, 3^’, 4^’-trimethoxy flavone (33) 5-hydroxy-7, 3^’-dimethoxy flavone (34) quercetin (1)

lonicerin (7)

48

49

Lonicera similis H^EMSL.

flower buds luteolin (8) quercetin (1)

50 Triterpenoids & Triterpenoidal saponins

Lonicera angustifolia leaves oleanolic acid (35) ursolic acid (36)

51 Lonicera burnei

H^EMSL.

flower buds oleanolic acid (35) bourneioside A (37) bourneioside B (38) bourneioside C (39) bourneioside D (40) bourneioside E (41)

52 53 54 55

Lonicera confusa DC.

flower buds hederagenin-28-O-β-D-glucopyranosyl (6→1)-O-β-D-glucopyranosyl ester (42)

hederagenin-3-O-α-L-arabinopyranosyl (2→1)-O-α-L-rhamnopyranoside (43)

macranthoside A (44) macranthoside B (45) dipsacoside B (46) macranthoidin A (47) macranthoidin B (48)

56

Lonicera fulvotomentosa H^SUETS.C. C^HENG

flower buds fulvotomentoside A (49)^* α-hederin (50)

sapindoside B (51)

57

Lonicera gracilipes var. glandulosa MAXIM.

fresh leaves ferna-7, 9 (11)-diene-3α, 16α-diol (52)

3α, 16α-dihydroxyferna-7, 9 (11)-dien-12-one (53)

58

ferna-7, 9 (11)-diene-3α, 16α, 19α-triol (54) 3α, 16α-dihydroxyfern-8-en-11-one (55) 3α, 16α-dihydroxyferna-8-ene-7,11-dione (56) Lonicera implexa

A^ITON.

leaves hederagenin-3-O-α-L-arabinopyranoside (57) 46 fresh aerial

parts

saponin 1-12(58-69) 63^*,66^*,68^*,69^* loniceroside A (70)^* loniceroside B (71)^*

59

60 fresh leaves saponin 1-4 (72-75)

74^*, 75^*

61 Lonicera japonica

T^HUNB.

flower buds 3-O-α-L-rhamnopyranosyl (1→2)-α- L-arabinopyranosyl hederagenin 28-O-β-D- xylpyranosyl (1→6)-β-D- glucopyranosyl ester (76)

3-O-L-arabinopyranosyl hederagenin 28-O- α-L- rhamnopyranosyl (1→2) [β-D-xylpyrano syl(1→6)]-β-D-glucopyranosyl ester (77) 3-O-α-rhamnopyranosyl (1→2)-α-L-arabino pyranosyl hederagenin 28-O-α-L- rhamno pyranosyl (1→2) [β-D- xylpyranosyl (1→6)]-β-D- glucopyranosyl ester (78)

3-O-[α-L-rhamnopyranosyl (1→2)-α-L-arabi nopyranosyl]-28-O-[β-D-glucopyranosyl (1→

6)-β-D-glucopyranosyl] oleanolic acid (79)

62

flowers dipsacoside B (46) macranthoidin A (47)^* macranthoidin B (48)^*

64

Lonicera nigra L. fruit

(berries) monodesmosidic saponins 1-5 (80-84)

bidesmosidic saponin (85-87) 65 Monoterpene

Lonicera nitida E. H. WILSON

fresh twigs leaves

lonitoside (88)^* 66

Lonicera xylosteum

L. leaves xylostosidine (89)

loxylostosidine A (90^*) loxylostosidine B (91)^*

67 68 69 Iridoid

Lonicera alpigena L.

fruits morroniside (92) kingiside (93)

alpigenoside (94)^*

70 68 Lonicera angustifolia leaves sweroside (95)

6^’-O-β-apiofuranosylsweroside (96)^* loganin (97)

52

Lonicera caerulea L.var.emphyllocalyx

fresh leaves 7-ketologanin (98) epi-vogeloside (99)

42

NAKAI. (6R, 9R)-3-oxo-α-ionol-β-D-glucoside (100) caeruleoside A (101)^*

caeruleoside B (102)^*

caeruleoside C (103)^* 71

Lonicera coerulea

L. fresh leaves

and stem bark

sweroside (95) loganin (97) secologanin (104) secologanic acid (105) loganic acid (106)

periclymenosidic acid (107)^*

72

Lonicera gracilipes var. glandulosa M^AXIM.

fresh leaves erythritol-1-O-(6-O-trans-caffeoyl) -β-D-glucopyranoside (108)

1,2,3,4-tetrahydroxy-2-methylbutane -4-O-(6-O-trans-caffeoyl)-β-D- glucopyranoside (109)

arabitiol-5-O-(6-O-trans-caffeoyl)- β-D-glucopyranoside (110)

73

Lonicera implexa A^ITON.

leaves sweroside (95) loganic acid (106) grandifloroside (111) vogeloside (112) epi- vogeloside (99)

74

fresh aerial

parts secologanin dimethyl acetal (113) vogeloside (112)

epi- vogeloside (99) loganin (97)

secologanin (104)

7-O-butylsecologanic acid (114) secologanin dibutylacetal (115) secologanic acid (105)

sweroside (95)

74

75 Lonicera japonica

THUNB.

young shoots

secoxyloganin (116) 76

flower buds loniceracetalides A (117) loniceracetalides B (118) loganin (97)

secologanin (104)

secologanin dimethyl acetal (113) secologanoside 7-methyl ester (119) sweroside (95)

vogeloside (112) 8-epiloganin (120) kingiside (93) morroniside (92) epi-vogeloside (99) dehydromorroniside (121)

77

78

stems＆

leaves

L-phenylalaninosecologanin (122) 7-O-(4-β-glucopyranosyloxy-3-methoxy benzoyl) secologanic acid (123)

6^’-O-(7α-hydroxyswerosyloxy)loganin (124) (E)-aldosecologanin (125)

(Z)-aldosecologanin (126)

79

Lonicera korolkovii S^TAPF.

young plants

korolkoside(127)^* 80

fresh fruits

morroniside (92) kingiside (93) loganin (97) 7-ketologanin (98) secoxyloganin (116)

secologanin dimethyl acetal (113)

81

secologanin (loniceroside) (104) sweroside (95)

83 68 Lonicera

morrowii A. G^RAY.

stems kinginoside﹝sweroside-6^’-O-(4^” -O-feruloyl)-α-L-rhamnoside﹞(128)

84

Lonicera

periclymenum L.

stems morroniside (92) secologanin (104) loganic acid (106) secoxyloganin (116) secologanoside (129) periclymenoside (130) loganin (97)

sweroside (95)

85 68

86

Lonicera

quinquelocularis

roots loganin (97) sweroside (93)

6^’-O-β-apiofuranosylsweroside (96)^*

86

Lonicera tatarica L. leaves loganin (97) secologanin (104)

50 Penylpropanoids

Lonicera gracilipes var. glandulosa MAXIM.

fresh leaves aseculetin-6-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranoside (131)

4,9,9^’-trihydroxy-3,3^’-dimethoxy-8- O-4’^'- neolignan-7-O-β-D-glucopyranoside (7S,8S-threo form) (132)^*

4,9,9’-trihydroxy-3,3^’-dimethoxy-8- O-4^’-neolignan-7-O-β-D-glucopyranoside (7S,8R-erythro form) (133)^*

7R,8R-threo-4,7,9,9’ -tetrahydroxy-3- methoxy-8-O-4^’-neolignan-3^’ -O-β-D-glucopyranoside (134)^*

7S,8R-erythro-7,9,9^’-trihydroxy-3,3^’- dimethoxy -8-O-4^’-neolignan-4-O-β-D-glucopyranoside (135)^*

4,7,9-trihydroxy-3,3^’-dimethoxy-8-O-4^’ -neolignan-9’^'-O-β-D-glucopyranoside (7R,8R-threo form) (136)

4,7,9-trihydroxy-3,3^’-dimethoxy-8-O-4^’ -neolignan-9’^'-O-β-D-glucopyranoside (7R,8R-erythro form) (137)

(6R,7E,9R)-9-hydroxy-4,7- megastigmadien -3-one-9-O-〔α-L-arabinopyranosyl-

Lonicera hypoleuca aerial parts 4-hydroxy-2,6-di-(4^'-hydroxy-3^'-methoxy)-

phenyl-3,7-dioxabicyclo-(3,3,0)octane (140) 90 Organic acid derivatives

Lonicera angustifolia leaves methyl-4-hydroxy benzoate(141) 51

Lonicera burnei HEMSL.

flower buds chlorogenic acid ethyl ester (142) bis (5-formylfurfuryl) ether (143) 5-hydroxymethyl-2-furaldehyde (144)

52 91

Lonicera caerulea L.var.emphyllocalyx N^AKAI.

fresh leaves protocatechuic acid (145) methyl chlorogenate (146)

42

Lonicera confusa DC.

flower buds chlorogenic acid (147) caffeic acid (148)

methyl chlorogenate (146)

5-O-caffeoyl quinic acid butyl ester (149)

43 92

Lonicera hypoleuca aerial parts syringic acid (150) 90 Lonicera implexa

AITON. leaves chlorogenic acid (147) macranthoin G

(3,5-dicaffeoylquinic acid methyl ester) (151)

74

Lonicera japonica

THUNB. flower buds chlorogenic acid (147) 3-caffeoyl-quinic acid (152)

3-caffeoyl-quinic acid methyl ester (153) 3,5-dicaffeoylquinic acid (154)

3,5-dicaffeoylquinic acid methyl ester (151) 3,5-dicaffeoylquinic acid butyl ester (155)^*

93 49

Lonicera macranthoid H^AND.-M^AZZ.

flowers macranthoidin F (156) macranthoidin G (157)

94

chlorogenic acid (147) 84

Lonicera similis H^EMSL.

flower buds caffeic acid (148)

3, 5-dicaffeoylquinic acid (154) chlorogenic acid (147)

95

Others

Lonicera angustifolia leaves β-sitosterol 51

Lonicera burnei H^EMSL.

flower buds β-sitosterol 52

Lonicera confusa DC.

flower buds β-sitosterol tetratriacontane

43 Lonicera hypoleuca aerial parts β-sitosterol

β- sitosterol glucoside n-nonacosanol

scopeletin

90

Lonicera implexa AITON.

leaves myoinositol 74

fresh leaves venoterpine 96

Lonicera japonica

THUNB. flower buds daucosterol sucrose

49

Lonicera

quinquelocularis

aerial parts β-sitosterol 1-inositol hexacosanol n-triacontanol nonacosane

95

Lonicera similis H^EMSL.

flower buds β-sitosterol nonacosanol nonacosane

95

* new compound

(二) 國內忍冬屬之研究現況

將國內現況分類為天然物化學研究(成分分離、結構鑑定)、品 質評估(藥材與複方)、藥理活性探討及藥品動力學探討；然而國內 對於忍冬屬之研究多以 Lonicera japonica THUNBERG為主，本文針對 忍冬屬天然物化學成分相關研究作整理，如Table2 所列：

Table 2 國內研究之忍冬屬植物化學成分

學名 部位 化學成分 來

源 Lonicera acuminata

WALLICH

(銳葉忍冬)

stems Long chain fatty acid and ester:

octacosanyl hexadecanoate Steroid:

phytosterol (campesterol, stigmasterol, β-sitosterol)

stigmast-5-ene-3β,7α-diol

stigmast-5-ene-3β,7β-diol sitosterol-3β-D-glucoside

sitosterol-3-β-D-glucoside-6'-acetate sitosterol-3-β-D-glucoside

Flavonoid:

isorhamnetin ochnaflavone quercetin

97

Organic acid derivative:

protocatechuic acid methyl caffeate chlorogenic acid methyl chlorogenate

3, 5-di-O-caffeoylquinic acid methyl 3, 5-di-O-caffeoulquinate 3, 4-di-O-caffeoylquinic acid methyl 3, 4-di-O-caffeoylquinate Flavonoid:

luteolin rutin

98 Lonicera japonica

T^HUNB. (忍冬)

flowers

Organic acid derivative:

chlorogenic acid

3, 5-di-O-caffeoylquinic acid Flavonoid:

luteolin

99

Organic acid derivative:

chlorogenic acid

4,5-di-O-caffeoyl quinic acid Cycloalkene:

sweroside Flavonoid:

luteolin

14

luteolin-7-O-α-L-rhamnopyranosyl (1→2)-β-D- glucopyranoside

luteolin-4’-methyl ether-7-O-α-L-

rhamnopyranosyl (1→2)-β-D-glucopyranoside apigenin-7-O-a-L-rhamnopyranosyl (1→2)-β-D- glucopyranoside

Lonicera japonica T^HUNBERG var.

Sempervillosa HAYATA

(毛忍冬)

flowers Long chain fatty acid and ester:

nonacosane hentriacontane

octacosanyl hexadecanoate tetracosanoic acid

docosanoic acid Steroid:

phytosterol (campesterol, stigmasterol, β-sitosterol)

100

在文檔中 紅腺忍冬葉部之化學成分研究; Studies on the Chemical constituents of the Leaves of Lonicera hypoglauca MIQUEL (頁 15-25)