source eich, of this pdf: eckart. 2008. solanaceae and...

4.2 Ergolines 225

Table 4.1 Unambiguously ergoline-positive Ipomoea species

Alkaloids identified in the seeds (TLC: comparisonIpomoea L. with authentic samples)a References

I. amnicola Morong. Clavines: 7 Amor-Prats and Harborne 1993aI. argillicola Clavines: 1, 4, 7 Amor-Prats and Harborne

R.W. Johnson Lysergic acid 1993a (TLC); Eich and Witte,amides: 14, 16 unpublished results (GC/MS)

I. aristolochiifolia Instead of TLC: HPLC McDonald 1982G.Don Clavines: 1, 7, 8

Lysergic acid amides: 16I. argyrophylla Vatke Clavines: 4 Isolation and structural

(syn.: I. jaegeri Lysergic acid amides: 17 elucidation of 4 and 17Pilger) Epigeal vegetative parts from the seeds:

(TLC and GC/MS): Stauffacher et al. 1965. Clavines: 1, 4 Epigeal vegetative parts: Eich and Lysergic acid amides: 14 Witte, unpublished resultsI. asarifolia (Desr). Clavines: 1, 7 Isolation and structural

R. & Sch. Lysergic acid amides: elucidation of 1, 14, 15 and14–16, ergobalansine ergobalansine from the seeds:

Jenett-Siems et al. 1994.All of these alkaloids Jirawongse et al. 1977; Kucht et al.

also present in the 2004; Steiner et al. 2006epigeal vegetative parts

I. cardiophylla A. Gray Instead of TLC: HPLC McDonald 1982 Clavines: 1, 7, 8 Lysergic acid

amides: 14, 16I. costata F. Muell. Clavines: 8 Amor-Prats and Harborne 1993a

ex Benth.I. diamantinensis Clavines: 7, 8 Amor-Prats and Harborne 1993a

J.M. BlackI. dumetorum Roem. Instead of TLC: HPLC McDonald 1982

& Schult. Lysergic acidamides: 14, 16

I. hildebrandtii Vatke Clavines: 5, cycloclavine Isolation and structural elucidation Epigeal vegetative of 5 and cycloclavine from the

parts (GC/MS): the seeds: Stauffacher et al. 1969.

Clavines: 4, 5, 7 Epigeal vegetative parts: Eich and Lysergic acid Witte, unpublished results

amides: 14I. imperati (Vahl) Clavines: 1, 8 Jenett-Siems 1996 b

Griseb. sub nom. Lysergic acidI. stolonifera J.F. Gmel. amides: 14

(continued)

4.2.3.1 4.1) (Table Species Ipomoea Ergoline-positive Unambiguously AsSurprisingly, ofprofile characteristic a show species Seventeen similar. very apparently are species these of profiles alkaloid the

doubt. any without ergoline-positive as considered be to are spp. Ipomoea 23 only present at mentioned, already

SOURCE Eich,

Handbook) (a Significance Economics and Biological Chemotaxonomy, Biosynthesis, Metabolites: Secondary Convolvulaceae:

and Solanaceae 2008. Eckart. PDF: THIS OF

226 4 Tryptophan-derived Alkaloids

I. jujujensis O’Donell Clavines: 1, 4, 7 Eich, unpublished results Lysergic acid

amides: 14I. leptophylla Torr. Clavines: 1 DerMarderosian 1967a; Chao and Lysergic acid DerMarderosian 1973b

amides: 14, 16I. marginisepala Instead of TLC: HPLC McDonald 1982

O’Donell Clavines: 1, 7, 8 Lysergic acid

amides: 14, 16I. minutiflora Instead of TLC: HPLC McDonald 1982

(M.Martens & Clavines: 1, 7, 8Galeotti) House Lysergic acid

amides: 14I. muelleri Benth. Clavines: 1–13, Isolation and structural

isopenniclavine elucidation of 1 and 14: Lysergic acid DerMarderosian et al. 1974.

amides: 14–16 Gardiner et al. 1965; Amor-Pratsand Harborne 1993a; Eich andWitte, unpublished results

I. orizabensis Clavines: 7 Perez-Amador et al. 1980;(Pell.) Led. Amor-Prats and Harborne 1993aex Steudl.

I. parasitica (H.B.K.) Clavines: 1, 7, 8 McDonald 1982 (HPLC), 1991;G.Don. Lysergic acid Amor-Prats and Harborne

amides: 14, 16 1993a, 1993bI. pedicellaris Benth. Instead of TLC: HPLC McDonald 1982 Clavines: 1, 7, 8 Lysergic acid

amides: 14, 16I. pes-caprae (L.) R.Br. Three unidentified Banerjee and Bhatnagar 1974;

ergolines Amor-Prats and Harborne 1993aI. pes-caprae (L.) R.Br. Clavines: 1 Mann 1997

ssp. pes-caprae Lysergic acidOoststr. amides: 14, 16

I. pes-caprae (L.) R.Br. Clavines: 1, 7 Isolation and structural elucidationssp. brasiliensis Lysergic acid amides: of 1: Kayser 1994.(L.) Ooststr. 14, 16, “ergotamine” Jirawongse et al. 1977; Henrici 1996

(see text) I. phyllomega (Vell.) Clavines: 1, 4, 7 Eich, unpublished results

House Lysergic acidamides: 14

I. setifera Poir. TLC and GC/MS: DerMarderosian 1967a; Clavines: 1, 4, 7 Schimming 2003 Lysergic acid (GC/MS); Eich,

amides: 14 unpublished results

Table 4.1 Unambiguously ergoline-positive Ipomoea species (continued)


(continued)

4.2 Ergolines 227

Table 4.1 Unambiguously ergoline-positive Ipomoea species (continued)


All of these alkaloids also present in theepigeal vegetative parts

I. tricolor Cav. TLC and GC/MS: Isolation and structural elucidation(syn.: I. violacea Clavines: 1–5, 7–9, 12, of 1, 7, 14, and chanoclavine-Iauct., non L.; chanoclavine-I acid acid: Hofmann andI. rubro-caerulea Lysergic acid Tscherter 1960;Hook.) amides: 14–16 Hofmann 1961; seeds: “badoh negro” Choong and Shough 1977.

Gröger 1963; Taber et al. 1963a;DerMarderosian et al. 1964;Genest 1965; DerMarderosianand Youngken 1966; Chao and DerMarderosian 1973b; McDonald 1982; Hahn 1990;Eich and Witte, unpublishedresults (GC/MS)

a Since 5R,8S-epimers of 5R,8R-lysergic acid derivatives are artefacts their occurrence is not mentioned beside the natural alkaloid, e.g., only ergometrine, not ergometrinineb I. stolonifera Poirs: no presence of ergolines in seeds and leaves (Jirawongse et al. 1977)

Key to the compounds1 = chanoclavine-I 10 = setoclavine2 = chanoclavine-II 11 = isosetoclavine3 = rac. chanoclavine-II 12 = penniclavine4 = agroclavine 13 = molliclavine5 = festuclavine 14 = ergine (lysergic acid amide)6 = dihydrolysergol-I (α-dihydrolysergol) 15 = lysergic acid 7 = elymoclavine α-hydroxyethylamide8 = lysergol 16 = ergometrine (ergonovine)9 = isolysergol 17 = ergosine

certain clavines and simple lysergic acid amides. The biogenetic route leading to lysergic acid derivatives suggests that these clavines in principal must be produced in every species in which lysergic acid amides are detectable. Thus, the detection of ergine and ergometrine in the case of I. dumetorum must include the production of these three true natural precursors although they were not detected in the respec-tive analysis. On the other hand, elymoclavine (or its isomer lysergol) is the only alkaloid identified in the remaining four species suggesting that these species do not show the total main alkaloid profile known from the other 19 species. Indeed a more simple profile might be given genetically. However, it should be taken into


account that in these four species additional TLC spots of apparent ergoline alka-loids have been observed which could not be identified due to the lack of authentic samples (Amor-Prats and Harborne 1993a). Thus, the TLC analysis of I. argillicolahad only shown elymoclavine beside two further unidentified ergolines in the study Amor-Prats and Harborne. The GC/MS analysis, a more sensitive method, used in a reinvestigation study led to the identification of chanoclavine-I, agroclavine, elymoclavine, ergine, and ergometrine (Eich and Witte, unpublished results). Thus, the “more simple chromatographic profile” (Amor-Prats and Harborne 1993a) of certain Ipomoea spp. might be only a question of the analytical sensitivities of the methods used, i.e., of a more or less excellent detection limit. Moreover, the most outstanding advantage of the GC/MS analysis is that this method includes the capa-bility to characterize the identity of every compound without any doubts on the basis of gas chromatography (retention time) and mass spectrum (parent peak, characteristic base and fragmentation peaks).These properties cause the superiority of GC/MS over TLC or HPLC.

Beside the main route precursors the other clavines found in different species are products of side routes also derived from:

● Chanoclavine-I, e.g., chanoclavine-I acid (Fig. 4.4)● Agroclavine, e.g., festuclavine, setoclavine, isosetoclavine (Fig. 4.8)● Elymoclavine, e.g., lysergol, dihydrolysergol-I, penniclavine, isopenniclavine

(Fig. 4.8)

These minor alkaloids have been detected especially in two species studied with particular intensity, i.e., I. muelleri Benth. and I. tricolor Cav. (Table 4.1).

Not more than two ergopeptines have been isolated and structurally elucidated unequivocally not only from an Ipomoea species but from a convolvulaceous species at all:

● Ergosine, which is also a minor constituent of Claviceps purpurea (Fig. 4.6), from the seeds of Ipomoea argyrophylla Vatke (Stauffacher et al. 1965)

● Ergobalansine/-inine (Fig. 4.6), a unique proline-free ergoline which is also a constituent of the fungal genus Balansia but has never been found in the genus Claviceps, from the seeds of Ipomoea asarifolia (Desr.) R. & Sch. (Jenett-Siems et al. 1994)

The surprising discovery of ergobalansine in a convolvulaceous species has consequences: in all those cases in which “ergosine” (Tables 4.1 and 4.4) or “ergot-amine” (Table 4.1) have been characterized only by TLC comparison with an authentic sample (e.g., Chao and DerMarderosian 1973b; Banerjee and Bhatnagar 1974; Wilkinson et al. 1986, 1987, 1988), reinvestigations seem to be necessary because these two proline-containing ergopeptines and its proline-free congener ergobalansine show very similar chromatographic behaviour (R

f values) with the

usual sorbents. Thus, many ergopeptine-positive results are not doubtful concern-ing the occurrence of this principal type of alkaloids at all but concerning the individual compounds. If ergopeptines are reported to be constituents of an

4.2 Ergolines 229

Ipomoea species or of any species of another convolvulaceous genus, especially Argyreia (see Table 4.4), these compounds are always minor metabolites. This might be the reason why they could not be detected in other ergoline containing species due to the lack of sufficient seed material. On the other hand, it might be that there are species which do not contain ergopeptines at all though being capable to synthesize clavines and simple lysergic acid amides. At least, this is the case within the fungal genus Claviceps since C. paspali in contrast to C. purpurea does not produce ergopeptines though being able to yield both other types of ergoline alkaloids.

As a matter of fact, the major alkaloids of mature ergot from C. purpurea, the ergopeptines ergotamine and the ergotoxine group (ergocristine, α-ergokryptine, β-ergokryptine, ergocornine), could not be detected in the Convolvulaceae. On the other hand, it is fascinating that almost all ergoline alkaloids ever detected in con-volvulaceous species had been already known from fungal genera. Only two ergoline alkaloids are confined to the Convolvulaceae family both discovered in an Ipomoea species:

● Cycloclavine, an isomer of agroclavine as well as a dehydrogenated derivative of festuclavine (Fig. 4.4), a unique metabolite of Ipomoea hildebrandtii Vatke(Stauffacher et al. 1969)

● Chanoclavine-I acid, a unique metabolite of Ipomoea tricolor Cav. (Choong and Shough 1977)

It can be concluded that the qualitative profile of ergoline alkaloid containing Ipomoea spp. is more or less identical with simple lysergic acid amides as major components and clavines as minor congeners. The only outstanding exception is represented by I. hildebrandtii. This species shows in its epigeal vegetative parts – in addition to the normal profile of clavines and simple lysergic acid amides – several novel unidentified clavines which could be characterized concerning their GC/MS data (Eich and Witte, unpublished results). However, the exact chemical structure of these novel clavines remains to be elucidated.

4.2.3.2 Contradictory Reports on the Occurrence of Ergoline Alkaloidsin the Seeds of Ipomoea species (Table 4.2)

Another group of Ipomoea species involves 15 species for which there are sin-gle positive reports concerning the occurrence of ergoline alkaloids. On the other hand, more convincing negative results have been reported for all of these species. The reasons for these doubtful cases have been already mentioned above. Moreover, several of these species meanwhile are characterized as syn-thesizers of two different alkaloid types: pyrrolizidines (I. coccinea, I. hederi-folia, I. lobata, I. quamoclit, I. × sloteri; see Sect. 3.7) and indolizidines (I. alba, I. turbinata; see Sect. 3.6). These findings may explain additionally certain errors of the past.


4.2.3.3 Ipomoea Species Apparently Devoid of Ergoline Alkaloidsin the Seeds (Table 4.3)

Table 4.3 summarizes 41 Ipomoea spp. for which only ergoline-negative reports have been published. Negative results are also important from the chemotaxonomic point of view. Tables 4.1–4.3 altogether include 79 out of about 650 species of this largest convolvulaceous genus. Twenty-three species only were found to be ergoline-positive (∼30%).

4.2.3.4 Ergoline-positive Argyreia species (Table 4.4)

The ergoline pattern of positive Argyreia spp. is very similar to the one found for Ipomoea spp. (Chao and DerMarderosian 1973b). Again ergine and chanocla-vine-I turned out to be the major alkaloids. It is remarkable that an ergopeptine could be detected in five out of 14 positive Argyreia spp. This has been character-ized as ergosine by TLC comparison with an authentic sample. However, due to reasons already explained above (see Ipomoea) it remains doubtful, if this com-pound has been really ergosine rather than a similar ergopeptine such as ergobalansine.

The Hawaiian baby wood rose, Argyreia nervosa (Burm. f.) Bojer, is the species most studied in the genus. Chemical analyses showed that the seeds contain the highest percentage of ergoline constituents (0.5–0.9%) of all posi-tive convolvulaceous species. Although the pericarp had shown the same alka-loid pattern as the seeds, the concentration was much lower (0.0015%). No alkaloids could be detected in the epigeal vegetative parts. The latter fact is also true for A. mollis. This is surprising since – in contrast to that – ergolines could be detected not only in the seeds but also in the epigeal vegetative parts of different Ipomoea spp. (Table 4.1) and Stictocardia tiliaefolia (Table 4.5), respectively. Another clavine-type alkaloid, lysergene (6-methyl-8-methylene-ergol-9-ene), not present in other convolvulaceous genera, could be identified in A. cuneata and A. nervosa (Table 4.4). Again this metabolite, a dehydration product of lysergol, was already known from Claviceps spp. (Hofmann 1964). The paleotropic genus Argyreia comprises about 100 spp. The percentage of species found to be ergoline-positive was higher than in the case of Ipomoea(14 out of 20 species checked).

4.2.3.5 Ergoline-positive Stictocardia and Turbina species (Table 4.5)

The paleotropic genus Stictocardia comprises only 11 species (Austin and Eich 2001). Four members, S. beraviensis, S. tiliaefolia, S. cf. laxiflora, and S. mojan-gensis have been screened for ergolines. With the exception of the latter species the analyses of the seeds yielded the typical clavines and simple lysergic acid amides of convolvulaceous species but no ergopeptines. The epigeal vegetative parts of the

4.2 Ergolines 231

Tabl

e 4.

2C

ontr

adic

tory

rep

orts

on

the

occu

rren

ce o

f er

golin

e al

kalo

ids

in th

e se

eds

of I

pom

oea

spec

ies

Ipom

oea

L.

Erg

olin

e-po

siti

ve r

epor

tsE

rgol

ine-

nega

tive

rep

orts

Eva

luat

ion

by t

he a

utho

r of

thi

s bo

ok

I. a

quat

ica

Fors

k.N

air

et a

l. 19

87

Jira

won

gse

et a

l. 19

77; A

mor

-Pra

ts

Pred

omin

antly

mor

e co

nvin

cing

neg

ativ

e re

port

s;an

d H

arbo

rne

1993

a; T

ofer

n 19

99;

in o

ne o

f th

ese

repo

rts:

epi

geal

veg

etat

ive

Schi

mm

ing

2003

m

ater

ial a

lso

nega

tive

(TL

C a

nd G

C/M

S)I.

cai

rica

(L

.) S

wee

t

Shar

da a

nd K

okat

e 19

79;

Jira

won

gse

et a

l. 19

77; O

debi

yiL

ike

I. a

quat

ica

(syn

.: I

. pal

mat

a Fo

rsk.

)aN

air

et a

l. 19

87

and

Sofo

wor

a 19

78; A

mor

-Pra

tsan

d H

arbo

rne

1993

a; K

ayse

r 19

94;

Schi

mm

ing

2003

I. c

arne

a ss

p. fi

stul

osa

(Mar

t.

Ban

erje

e an

d B

hatn

agar

Ji

raw

ongs

e et

al.

1977

; Per

ez-A

mad

or

Tho

ugh

ther

e is

eve

n a

repo

rt o

n th

e is

olat

ion

and

ex C

hoi

sy) D

.F. A

ust

in19

74; U

mar

et a

l.et

al.

1980

; Am

or-P

rats

and

Har

born

e un

ambi

guou

s st

ruct

ural

elu

cida

tion

of19

80 (

leav

es)

1993

a; W

eigl

199

2; M

ann

1997

fe

stuc

lavi

ne a

nd d

ihyd

roly

serg

ol-I

(e

pige

al v

eget

ativ

e pa

rts)

; (=

α-di

hydr

olys

ergo

l) f

rom

the

leav

es

Schi

mm

ing

2003

(U

mar

et a

l. 19

80),

ther

e ar

e m

any

nega

tive

repo

rts

incl

udin

g T

LC

and

GC

/MS

of th

e le

aves

. A m

isid

entif

icat

ion

of th

e sp

ecie

san

alys

ed b

y U

mar

et a

l. m

ight

be a

n ex

plan

atio

nb

I. c

occi

nea

L. (

syn.

: G

röge

r 19

63; P

erez

-Am

ador

B

eyer

man

et a

l. 19

63;

Pr

edom

inan

tly m

ore

conv

inci

ng n

egat

ive

Qua

moc

lit

cocc

inea

et

al.

1980

; Wilk

inso

n D

erM

arde

rosi

an 1

964;

re

port

s; e

pige

al v

eget

ativ

e m

ater

ial

Moe

nch

)aet

al.

1987

G

enes

t and

Sah

asra

budh

e w

as a

lso

nega

tive

(TL

C a

nd G

C/M

S);

1966

; Am

or-P

rats

and

Har

born

e

real

alk

aloi

dal c

onst

ituen

ts:

1993

a; J

enet

t-Si

ems

et a

l. 20

05

pyrr

oliz

idin

es (

see

Sect

. 3.7

)I.

hed

erac

ea (

L.)

Jac

q.

Wilk

inso

n et

al.

1986

B

eyer

man

et a

l. 19

63;

Lik

e I.

aqu

atic

aD

erM

arde

rosi

an 1

964;

Am

or-P

rats

and

Har

born

e 19

93a;

Eic

h, u

npub

lishe

d re

sults

(con

tinue

d)


I. h

eder

ifol

ia L

. [sy

n.:

Nai

r et

al.

1987

;D

erM

arde

rosi

an a

ndL

ike

I. c

occi

nea

I. a

ngul

ata

Lam

.;Q

uam

ocli

tW

ilkin

son

et a

l. 19

87

You

ngke

n 19

66; D

erM

arde

rosi

anan

gula

ta (

Lam

.) B

ojer

]19

67b;

Am

or-P

rats

and

Har

born

e19

93a;

Jen

ett-

Siem

s 19

96; J

enet

t-Si

ems

et a

l. 19

93, 1

998,

200

5I.

lac

unos

a L

. W

ilkin

son

et a

l. 19

86

N

o ne

gativ

e re

port

ava

ilabl

e; n

ever

thel

ess

doub

tful

sinc

e th

e m

ajor

ity o

f th

e ot

her

spec

ies

repo

rted

to b

e er

golin

e-po

sitiv

e in

the

pape

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thes

e au

thor

s (W

ilkin

son

et a

l. 19

86,

1987

, 198

8) a

re e

valu

ated

pre

dom

inan

tly a

ser

golin

e-ne

gativ

e in

this

tabl

eI.

lob

ata

(Cer

v.)

Th

ell.

W

ilkin

son

et a

l. 19

88

Jene

tt-Si

ems

et a

l. 19

99, 2

005

Pred

omin

antly

mor

e co

nvin

cing

erg

olin

e-ne

gativ

e[s

yn.:

Qua

moc

lit

loba

ta

re

port

s al

so in

clud

ing

epig

eal v

eget

ativ

e(C

erv.

) H

ouse

,Min

am

ater

ial (

TL

C a

nd G

C/M

S); r

eal a

lkal

oida

llo

bata

Cer

v.]

cons

titue

nts:

pyr

roliz

idin

es (

see

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. 3.7

)I.

nil

(L

.) R

oth

[sy

n.:

Nai

r et

al.

1987

; D

erM

arde

rosi

an 1

964,

196

7b;

Pred

omin

antly

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e co

nvin

cing

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e-ne

gativ

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harb

itis

nil

Der

Mar

dero

sian

and

You

ngke

n re

port

s, s

omet

imes

eve

n w

ith m

ore

than

one

(L.)

Ch

oisy

]19

66; G

enes

t 196

5; G

enes

t and

pr

oven

ance

or

culti

var

(e.g

., 5

culti

vars

Saha

srab

udhe

196

6; A

mor

-Pra

ts

nega

tive

in o

ne r

epor

t); e

pige

al v

eget

ativ

ean

d H

arbo

rne

1993

a;m

ater

ial a

lso

nega

tive

(TL

C a

nd G

C/M

S)Sc

him

min

g 20

03I.

pur

pure

a (L

.) R

oth

Ta

ber

et a

l. 19

63a;

Hyl

in

Bey

erm

an a

nd v

an d

e L

inde

L

ike

I. n

ilan

d W

atso

n 19

65; N

ikol

in

1963

; Der

Mar

dero

sian

196

4,an

d N

ikol

in 1

971;

19

67b;

Der

Mar

dero

sian

and

Wilk

inso

n et

al.

1986

Y

oung

ken

1966

; Gen

est 1

965;

Gen

est a

nd S

ahas

rabu

dhe

1966

;H

ahn

1990

; Am

or-P

rats

and

Har

born

e 19

93a;

Sch

imm

ing

2003

Tabl

e 4.

2C

ontr

adic

tory

rep

orts

on

the

occu

rren

ce o

f er

golin

e al

kalo

ids

in th

e se

eds

of I

pom

oea

spec

ies

(con

tinue

d)

Ipom

oea

L.

Erg

olin

e-po

siti

ve r

epor

tsE

rgol

ine-

nega

tive

rep

orts

Eva

luat

ion

by t

he a

utho

r of

thi

s bo

ok

4.2 Ergolines 233

Tabl

e 4.

2C

ontr

adic

tory

rep

orts

on

the

occu

rren

ce o

f er

golin

e al

kalo

ids

in th

e se

eds

of I

pom

oea

spec

ies

(con

tinue

d)

Ipom

oea

L.

Erg

olin

e-po

siti

ve r

epor

tsE

rgol

ine-

nega

tive

rep

orts

Eva

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Table 4.3 Ipomoea species apparently devoid of ergoline alkaloids

Absence of ergolinesa

Ipomoea L. Seeds EVPb Roots References

I. alba L. x x x DerMarderosian and Youngken 1966; DerMarderosian 1967b; Tofern 1999

I. adenoidesSchinz.

x n.d. n.d. Amor-Prats and Harborne 1993a

I. albivenia(Lindl.)Sweet


I. arborescensSweet

x x x DerMarderosian and Youngken 1966; Eich, unpublished results

I. batatas Lamk. x x x Jirawongse et al. 1977; Tofern 1999I. batatoides

Choisyx x n.d. Eich, unpublished results

I. bonariensisHook.

x x n.d. Eich, unpublished results

I. bracteata Cav. x n.d. n.d. Amor-Prats and Harborne 1993aI. chloroneura

Hall. f.x n.d. n.d. Amor-Prats and Harborne 1993a

I. coptica (L.) Roem. & Schult.

x x n.d. Amor-Prats and Harborne 1993a; Eich and Witte, unpublished results

I. coscinospermaHochst. ex Choisy


I. cynanchifoliaMeissn.


I. eremnobrochaD.F. Austin

x n.d. x Tofern 1999

I. eriocarpa R. Br. x n.d. n.d. Amor-Prats and Harborne 1993a; Eich,unpublished results

I. gracilisepalaRendle


I. graminea R. Br. x n.d. n.d. Amor-Prats and Harborne 1993aI. hochstetteri

Housex n.d. n.d. Amor-Prats and Harborne 1993a (2 provenances)

I. indica Burm. x x n.d. Amor-Prats and Harborne 1993a (2 provenances); Schimming 2003 (2 provenances)

I. involucrataBeauv.

x x n.d. Weigl 1992; Schimming 2003

I. lindheimeriA. Gray

x n.d. n.d. Der Marderosian 1964; DerMarderosian and Youngken 1966; Genest and Sahasrabudhe 1966; Amor-Prats and Harborne 1993a

I. mauritaniaJacq. (syn.: I. digitata L.)

x x n.d. Jirawongse et al. 1977; Schimming 2003

I. meyeri(Spreng.)G. Don

x x x Tofern 1999

I. microsepalaBenth.

x n.d. n.d. McDonald 1982; Amor-Prats and Harborne 1993a

(continued)

I. mirandina(Pittier)O’Donell

x n.d. n.d. Eich, unpublished results

I. murucoidesRoem. & Schult.


I. obscura (L.) Ker-Gawl.

x x x Jirawongse et al. 1977; Weigl 1992; Amor-Prats and Harborne 1993a; Schimming 2003

I. pedatisectaMart. & Gawl.


I. pilosa c x n.d. n.d. Banerjee and Bhatnagar 1974I. plebeia R.Br. x x x Amor-Prats and Harborne 1993a (2 provenances);

Schimming 2003I. ramosissima

Choisyx x x Amor-Prats and Harborne, 1993a; Schimming

2003I. regnellii Meisn. x x x Mann 1997I. reptans Poirs x x n.d. Jirawongse et al. 1977I. reticulata

O’Donellx x x Tofern 1999

I. rubens Choisy x x x Weigl 1992I. sepiaria Koen.

ex Roxb. (syn.: I. maxima G. Don)

x x x DerMarderosain and Youngken 1966; Schimming 2003

I. setosaKer-Gawl.

x n.d. n.d. Eich, unpublished results

I. shirambensisBak.

x x n.d. Amor-Prats and Harborne 1993a; Jenett-Siems and Eich, unpublished results

I. triloba L. x x x DerMarderosian and Youngken 1966; Kayser 1994; Eich, unpublished results

I. verbascoideaChoisy


I. violacea L.d

[syn.:I. macranthaRoem. & Schultes;I. tuba(Schltdl.)G.Don]

x x n.d. Tofern 1999

I. wightii (Wall.)Choisy

x x n.d. Amor-Prats and Harborne 1993a; Schimming 2003

a Checked by comparison with authentic samples by means of thin-layer chromatography (TLC) and/or quantitative colorimetric analyses with van Urk’s reagent; × = absent; n.d. = not determinedb EVP = epigeal vegetative partsc No species authority in the original report; thus, a correct assignment is impossible since three authors are available: Cav. vs. Houtt vs. Sweetd Not to be mixed up with I. violacea auct., non L. (syn.: I. tricolor Cav.)

Table 4.3 Ipomoea species apparently devoid of ergoline alkaloids (continued)Absence of ergolinesa

Ipomoea L. Seeds EVPb Roots References


Argyreia Lour.

Alkaloids identified in the seeds (TLC: comparison with authentic samples)a References

A. acuta Lour.b Clavines: 1 DerMarderosian 1967a; Chao andLysergic acid amides: 14, 16 DerMarderosian 1973b

A. barnesii(Merr.)Ooststr.

Clavines: 1 – 3, 5, 7, 9Lysergic acid amides:

14 – 16

DerMarderosian 1967a; Chao andDerMarderosian 1973b

A. cuneataKer-Gawl.

Clavines: 1 – 12 Chao and DerMarderosian 1973b

A. hainanensisc Clavines: 1 DerMarderosian 1967a; Chao andLysergic acid amides: 14, 16 DerMarderosian 1973b

A. hookeriC.B.Clarke

Clavines: 1, 7Lysergic acid amides: 14

Eich, unpublished results

A. luzonensis(Hall. f.) Ooststr.

Clavines: 1 – 5, 7 – 9, 12Lysergic acid amides: 17

Chao and DerMarderosian 1973b

A. mollis (Burm.f.) Choisy

Clavines: 1 – 5, 7, 9, 12Lysergic acid amides: 17

Chao and DerMarderosian 1973b; epigeal vegetative parts and roots: negative, Tofern et al. 1999

A. nervosa (Burm.f.) Bojer

Clavines: 1 – 13; in addition to TLC also infrared spectra (IR) for 4 – 7, 10, 11

Lysergic acid amides: 14,in addition to TLC also infrared spectrum (IR)

Isolation and structure elucidation of 14:Miller 1970. Hylin and Watson 1965; DerMarderosian 1967a; McJunkins et al. 1968; Chao and DerMarderosian 1973a,b; epigeal vegetative parts and roots: negative, Tofern et al. 1999

A. obtusifoliaLour.

Clavines: 1 – 3, 5, 7, 12Lysergic acid amides:

14 – 17

DerMarderosian 1967a; Chao and DerMarderosian 1973b

A. philippinensis(Merr.)Ooststr.

Clavines: 1, 3, 5, 8, 9, 12Lysergic acid amides:

14 – 17

Chao and DerMarderosian 1973b

A. ridleyi (Prain)Prain ex Ooststr.

Lysergic acid amides: 17 Chao and DerMarderosian 1973b

A. rubicundaChoisy

Clavines: 8 Chao and DerMarderosian 1973b

A. splendens(Hornem.)Sweet

Clavines: 1, 2, 5, 7, 8Lysergic acid amides: 17


A. wallichiiChoisy

Clavines: 1, 5, 9,Lysergic acid

amides: 14, 16


a Since 5R,8S-epimers of 5R,8R-lysergic acid derivatives are artefacts their occurrence is not mentioned beside the natural alkaloid, e.g., only ergometrine, not ergometrinineb Species authority given in the original report is not correct.

Table 4.4 Unambiguously ergoline-positive Argyreia species

(continued)

4.2 Ergolines 237

c Species authority neither given in both original reports nor to be found in the data base of the International Plant Name Index (IPNI; Kew Botanical Gardens et al.) and the w3TROPICOS Nomenclatural Database (Missouri Botanical Gardens), respectively

Key to the compounds:The key is identical to the one of Table 4.1 except compound 6 (dihydrolysergol-I has not been detected in the genus Argyreia; instead lysergene has got this number here)1 = chanoclavine-I 10 = setoclavine2 = chanoclavine-II 11 = isosetoclavine3 = rac. chanoclavine-II 12 = penniclavine4 = agroclavine 13 = molliclavine5 = festuclavine 14 = ergine (lysergic acid amide)6 = lysergene 15 = lysergic acid α-hydroxyethylamide7 = elymoclavine 16 = ergometrine (ergonovine)8 = lysergol 17 = ergosine9 = isolysergol

Table 4.4 Unambiguously ergoline-positive Argyreia species (continued)

first two species turned out to contain a similar pattern; whether this is also true for the third remains unknown. Only two species of the pantropical genus Turbina (15 spp.) have been checked for the presence of alkaloids in the seeds. Beside the famous, originally neotropical, woody liana T. corymbosa (seeds: ololiuqui) with meanwhile pantropical distribution the again neotropical T. abutiloides is also ergo-line-positive. In both species the alkaloid profile is a typical convolvulaceous one: certain clavines and simple lysergic acid amides; no ergopeptines have been detected. Like in the case of those Argyreia spp. whose seeds have turned out to contain ergolines, these alkaloids were not found in the epigeal vegetative parts of T. abutiloides.

4.2.3.6 Intrafamilial Distribution and Chemotaxonomic Significance

The unambiguous occurrence of ergoline alkaloids in the Convolvulaceae family is confined to the traditional genera Argyreia, Ipomoea, Stictocardia, and Turbina,respectively. These four genera belong to the Ipomoeeae, the most advanced con-volvulaceous tribe (Stefanovic et al. 2002, 2003). Since the other 11 tribes of the family as well as the sister family, the Solanaceae, are lacking such metabolites these apomorphic characters are of important chemotaxonomic significance though only on this higher taxon level.

The infrageneric distribution within Ipomoea is of a limited value from the chemotaxonomic point of view. There are ergoline-positive species in four out of seven traditionally accepted subgenera (Verdcourt 1963; Austin and Huáman 1996). In the case of subgenus Ipomoea they are confined to one section out of two, in the case of subgenus Quamoclit to three sections out of six. Within the subgenus Eriospermum comprising most of the known ergoline-positive species (12) these are distributed between two out of three traditional sections:


Alkaloids identified in the seeds (TLC:comparison with authentic samples)a References

Stictocardia Hall. f.S. beraviensis (Vatke)

Hall. f.Clavines: 1, 7Lysergic amides: 14, 15


S. tiliaefolia (Desr.) Hall.f. [syn.: S. campanu-lata (L.) Merr.]

Clavines: 1, 2, 6 – 9, 12,isopenniclavine

Lysergic acid amides: 14, 16

Isolation and structural elucidation of 8 from epigeal vegetative parts: Schimming 2003.

DerMarderosian 1967a; Chao and DerMarderosian 1973b; Lee et al. 1979 b

S. cf. laxiflora (Baker)Hall. f.

Clavines: 1, 7Lysergic acid amides:

14, 15


Turbina Raf.T. abutiloides (H.B.K.)

O’DonellClavines: 1, 4, 7Lysergic acid amides

14 – 16

Eich, unpublished results; epigeal vegetative parts and roots: negative, Mann 1997

T. corymbosa (L.) Raf.[syn.: Rivea corymbosa(L.) Hall. f.]

seeds: “ololiuqui”

Clavines: 1, 7, 12Lysergic acid amides:

14, 16

Isolation and structural elucidation of 1, 7, 14: Hofmann and Tscherter 1960; Hofmann 1961.

Taber et al. 1962; 1963b; DerMarderosian et al. 1964; Genest 1965; Genest and Sahasrabudhe 1966; DerMarderosian and Youngken 1966 (3 provenances); DerMarderosian 1967a and references therein

a Since 5R,8S-epimers of 5R,8R-lysergic acid derivatives are artefacts their occurrence is not mentioned beside the natural alkaloid, e.g., only ergometrine, not ergometrinineb Identification of all ergolines by isolation and comparison with authentic samples by means of two dimensional thin-layer chromatography (2D-TLC)

Key to the compounds:The key is identical to the one of Table 4.1; however, only compounds in bold have been detected in the genera Stictocardia and/or Turbina1 = chanoclavine-I 10 = setoclavine2 = chanoclavine-II 11 = isosetoclavine3 = rac. chanoclavine-II 12 = penniclavine4 = agroclavine 13 = molliclavine5 = festuclavine 14 = ergine (lysergic acid amide)6 = dihydrolysergol-I (a-dihydrolysergol) 15 = lysergic acid a-hydroxyethylamide7 = elymoclavine 16 = ergometrine (ergonovine)8 = lysergol 17 = ergosine9 = isolysergol

Table 4.5 Unambiguously ergoline-positive Stictocardia and Turbina species

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