Plant Alkaloids: A Guide to Their Discovery and Distribution

147 Pages·1996·42.48 MB·English

by  Robert F Raffauf

FOOD PRODUCTS PRESS
Plant Alkaloids
An Imprint of The Haworth Press, Inc.
Herbs, Spices, and Medicinal Plants
A Guide to Their Discovery
Lyle E. Craker, PhD
Senior Editor
and Distribution
Plall' Alkaloids: A Guide 10 Their DiscovelY and Distribution
by Robert F. Raffauf
Herbs, Spices, and Medicinal Plams: Recent Advallces
ill BolallY. Horticulture, alld Pharmacology.
Volumes 1-4, edited by Lyle E. Craker and James E. Simon
Robert F. Raffauf, FLS, FMAS
Related lilies of interest from Food Products Press:
Opillm Poppy: BotollY, Chemistry, and Pharmacology
by L. D. Kapoor
The HOllest Herbal: A Sensible Guide [0 the Use of Herbs
and Related Remedies, Third Edition by V<lITO E. Tyler
Herbs ojC/lOice: 71!e 711erapelltic Us'e ojP hytomedicil/a/s
by ValTo E. Tyler
Food Prodltcts Press
An l!nprinl of The H<lwOrlh Press, Ine.
New York. London
CONTENTS
Foreword
VII
Richard EVQ1ls Schultes
Preface IX
Alkaloid Test Results
Appendix 225
Bibliography 229
Generic Index 231
Published hy
. i"ood Produels l'Tess, a~ imprint "fThe Haworth "ress, 11Ie .. 10 Alice Sired.. Binghamton, NY
13904·1580
t) 1996 by The Ilaworth Press, lite. All righls reserved. No pm! of Ihis wurk n~ly be rCllfoduccd
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in writing {Iurn Ihe J)ubli>h~r, J>rin\L'd in tlie Uniled SiDles uf Amerrca.
Ralfaur, nober! F. (Koher! I'mucis). 1916-
l)l~nl alkaloids 11 guide to their discovery and dislri\)lIlion { Robert F. Rllilnuf.
p. em.
Includes hihliogmphicallclcrcnccs (p. ) ~nd ilideA.
ISBN 1·56022·860· I (Ilk. paper)
I. Alkaloids. 2. BQ(nnical chemislry.1. Tille.
QKK98.MIOS 1996
581.19'242ok20 90·5319
CII'
Foreword
ABOUT HIE AUTUOI!
Robert F. Raffauf, PhD, is Professor Emeritus of Phannacognosy
During scveral years of field work in the Northwcst AI~lazoni~, I
and Medicinal Chemistry at Northeastern University in Boston. lie
lived and worked with members of many of the AmaZOnian Indian
currently hollis an appointment as Research Associate at the Botani
tribes. Il was an extraordinary opp0l1unity 10 obsclve, apprcciate,
cal Museum of Harvard University, where he has also taught Ilc
and record their local customs, rituals, and particularly, as a botanist,
has served as Visiting Professor at the School of Pharmacy at the
their intelligent uses of the plants of the forests in which they lived.
University of Puerto Rico and al the School of Biological Sciences
The imp0l1ance oflhis information, beyond simply creating an inter
of lhe National Polytechnic Institute of Mexico. Dr. Ranilllf has led
esting ethnobotanieal record, was not entirely obviolLs at the time.
numerous expeditions in Illany paris of the world in the SC:U'C~l for Aficr my return to more academic pursuits, I met the author·of
new plants of pOIe ntia I medicinal value and has lectured extenSIvely
the following pages, then a chemist for II major North American
on this and related matters, including the rain forests and conserva
pharmaceutical compnny, with an interest primarily in that portion
tion. lie is the author of eight books, 69 journal publications, and
of my notes denling with the treatment of disease as it WHS under
four patents, and he continues to work with graduate students inter
stood by the Indian peoples. Some philliS, it was thought, could be
ested in natural products research. A 50-year member or the Ameri
sources of new chemical compounds lor cventual use in our own
can Chemical Society, Dr. RafTauf is <llso a Fellow of the Linncan
system of medicine. Furthermore, in (In ut~Clllpl to reach that g?(lI,
Society of London and of the American Association of Advance
the addition of chemical and phannacologlc(li data to thc botalllcal
ment of Science. In 1988, he was awarded an appointment as Resi
record would expand our knowledge of the rain forest and its plant
dent Scholar at the Rockefeller Study Center in Bellagio, Italy.
ami <lIlimal inhabitants. A collaboration seemed a natural and log
ical consequence.
As a result of the work described in this book, many plants have
been the subjects of further botanical, chemical, and phalmncologi
cal research. This integrated, interdisciplinary approach has been of
great advantage to our students, thosc in my cO~lrses at Harvard
University as well as those of Professor Raffaul at t:'!011heastern
University. A number of our students have even carncd out field
work in variolls parts of tropical A1I1erica. With them we have been
able to co-author a number of technical papers on aspects of the
wealth of natural resources in the Western Amawll and to supply
them with challenging problems in the numerous disciplines bear
ing on rain forest science. Together we have published two books
(The Healillg Forest, Ville 0/ tli"e SOIlI) extending our knowledge of
the biodiversity of this vast area of So lith America.
•
1'11/ PLANT ALKALOIDS
It is Ollr hope that the inFonnation which my colleague has as~
sembled here will continue to encourage academic as well as com~ Preface
mercial research on the uselulncss of plants to humans and contrib~
ute to current efforts at conservation of Amazonian resources, some
of which are on the verge of extinction as a result of continued
uncontrolled devastation in many areas of these marvelous forests.
The senrch for plant alkaloids ofnovcl chemical structure having
~Richard Evans Schultes. PhD. FMLS
potential value as medicinal agents, as toxic principles, or as ap~
Jeffrey Professor of Biology.
propriate starling materials for synthetic modification leading to
Emeritus Direc!OI; Botanical Museum,
other useful products, has occupied the attention of phytochemisls
Harvard University,
for over 150 years. In 1950, about 2,000 of these substances were
Cambridge, Massachusetts
recognized; by 1970 this number had increased to about 4,000 and
20 years later 10,000 were known .. In recent times, they have been
considered as uscthl taxonomic markers in attempts to construct
more "natural" systems of plant classification through chemotax~
onomy, and as suitable substances for the study of biosynthctic
pathways in plant metabolism. During the laller part of the present
century, emphasis on the conservation of plant resources and the
ethl1obotanical information concerning their use by many of the
world's aboriginal societies has given added impetus to the impor~
tance of the continued study of the "chemical factory," represented
by the large unexploited portion of the plant kingdom before much
or it disappear!> under the pressures incident to the mass movements
of peoples and the increase in the world's population. Both lire in
large part responsible for devastation of many noms, particularly
those of the rain forests. Not only will a number of species be lost
even before they arc known and named by botanists, but litemlly
thousands of chemical compounds new to science will disappear
forever.
During the past 40 years I have been involved, in one way or
another, with the screening of several thousand plants for the presence
of alkaloids as potential medicinal agents under the auspices of a
number of governmental, industrial, and academic institutions. Under~
lying this activity has been the hope thai the discovery of new eom~
pounds of this class would lead to substances at least as usefi.1 as tJlose
which similar studies have produced in the pasL. This screening has
been done on lI·esh plant material in the field, on small quantities laken
ix
PLAN1'ALKALO/VS Pre/act!
fmrn hcrbmium specimcns, and in thc laboratOty using a few grams of then, not an infallible result (Abisch and Reichstein, 1960). Fal~c
dricd malerialmade available by bot.anists, colk"Ctors, herb dcalers, and positivc tests arc given by many Iypes ofnollalkal~idal plant con~ht.
my personal collections in many p<u1S of the world. uents with a variety of alkaluidal rcagents (Habib, ~980). Ballck.
Variolls methods for the screening of largc numbers of plant Rivier and Plowman (1982) have pointed out the Importance of
samplcs for alkaloids have been lIsed by many investigators more or methods used in field drying lind preservation of herbar!um speci·
less sliccessfully (Famsworth, 1966). Seveml of thcse were used, mens with respect to the reliability of the result~ obtamcd when
depending on the facilities available at the time, but most of the tcsting them. A plea for such testing nnd a revt~w of the .n~ore
results reported herein were obtained by simplc methods described elegant methods for its accomplishment has been given. by Plllllp~·
some years ago (RarTauf, 1962a; RafTauf and Altschul, 1968). In the son (1982). Furlhennore,lIs every plant collector has (llscovered, It
field, these involve spoiling a droplet of plant sap on filter paper and
is not always practical in a given instance to collect all oftl~e parts of
applying a droplet of DmgcndorfT's rcagcnt; the development of II a plant in which alkaloids may occur. Nonetheless, an estimated 85
red·onlllge color iwJicates the presence of alkaloids. In the laboralo·
percent ofnlkaloid·colltaining plants can bc d~tcctcd by the methods
ry or herbarium, simplc extracts of dried plant material may bc used, described here; a number of known alkalOidal plants have b~en
with certain limitations, for thc samc purpose (Balick, Rivier, and
included in thc survcy to serve us controls. . '
Plowman, 1982).
Ilerbarium specimens representing otherwise relatively Inacces·
Methods may be adapted to needs of the investigator; tests for somc
sible specics of several families (Apocyno~eac, Bomba~aceac, L~.
specific types of nitrogenolls compounds may be included (e.g .• in·
copodiaceae, Lytliraceae, Orchidaceae, Rubtaceae) wcr~ mdudc,d III
doles. simplc amines. and amino acids). All npproximation of the
Ihis survey. Small samples were selected fr~)1n sheets III the. Gra~.
quantity of alkaloid in n sample may be made by compming the
Oakes Ames, and Arnold Arborctum herb<lna of Ilarvard Untvers~·
intensity of the color produced in thc DragendorfT test with those
ty under the guidance of Professor Richard Evan~ Schul~es, Emen
produced by standard alkaloid solutions of known concentratioll. fiy
tus Director of the Botanical Museum, whose assistance IS grateful·
using the Dragcndorn' fC.lgent as a spray, it is also possible 10 conduct
thin-layer chromatographic studies in the ficld. Several yt..'ars ago, in an Iyacknowledged. .
Not all of this testing was done by me; some of It was done by
attempt to devise a method for the idenlification of specific compounds
anthropologists, ethnobotanists, ~Ild pl,allt col.lectors in the course of
in a particular alkaloid-positive collection, 11 pol1able laooratOlY was
field work sponsored by academiC or IIldUSlrllll programs und~r .my
assembled for the evaluation of small extracts of fresh plant material
by chromatographic analysis using alumina-coated microscope slides direction some by laboratory technicians under my supcrvlsl~n,
and samples of the alkaloids expected to be prescnt. In the course of somc by' fonner students as preliminary exerci~s ill phytochelnls·
the study, it was found that some of the compounds were present only try, and some in collaboration with phytochemical. programs sup
during a re:'itlicted portion of the plant's growth cycle. We now know porled by the COlilicils of Scientific and lndustnal Resenrch of
that, in some cases at least, alkaloids are indeed further modi lied by the Australia and South Africa. Portions of the test rcsults from these
plants thnl produce them. pmgrams which had been at my disposal, I~ave been include~l he.re
An advantage of these simple methods is {Iwt they allow such for completencss in order to cOllvey some Idea of the alkal?ld diS·
studies to bc done far Irom a source of electric power and other tribution in plant families represented in the southern hel~lsph~re.
amenities oflhe laboratory. But it is also tme thutthcre arc a Ilumber Further data 011 these studies,.as well as the results of the Isolation
ofullcertainties in such procedures; nol al! nitrogcl1-eontninillg sub and pharmacological testing of a large number of nlkaloids, arc to be
stances will react with either DragendortT's or Mayer's reagent. A fOllnd in a rccent excellent publication by the Melbourne group
ballery of test reagents would give a more definitive although, even (Coliins et aI., \990).

ALKALOID TEST RESULTS
A
ACANTHACEAE
346 gelJcl'U; 4,300 species
This is a pantropical family with four centers of diversification:
Amazon, Central America, Africa, and Indo-Malaysia. Its c1assili
cation has not been. and may not yet be, a mallcr of agreement
among taxonomists, but althe momenllhc family wOllld seem to be
divided into three subfamilies with a close relationship of several
members to the Scrophulariaceac. Some members arc cuhivated as
ornamentals.
Alkaloids have been detected previously in a few genera. In this
study of about 400 samples representing 297 species, six known
alkaloidal species were included: Acanthus ilicifolius (1/2), Adha!o
da vasica, Anisoles sessi/ijlorus, f-lypoestes verticillaris (2/4), Macro
rtmgia /ungistrobus, Rhinacont/lIls commllnis (112).
Alkaloids were also detected in the following: Angkafal1thus
lrQl1SVaafeflsis (2/2), Allisacaflthus illsignis, Aphelaf/dra deppeana
(1/4), Asystasia atripficiJolia, A. we/wifchii, Barfel'ia matopoellsis,
B. Ivlllndi/o!ia, B. sinensis, Blechllln pyramidalum (113), Blepha!'is
boerhaaviJolia, B. 11/argillata, B. lIatalensis, Btephan's sp., Cmss(fn
dra spinescens, Dicfiptera cfinipodio, Duvemoya (= Justicia) aco
ni/iJolia, D. adhatoides (1/2), Dyscho!'iste hirsutissimo (1/4), Ecbo
lium sp., Elylraria acaulis, E. squamosa (3/3), Hellligmphis hirta
(whole plant), I-1emigmphis spp. (2/2), Hypoesfes aristata (113),
Jacobinia (= Jlls/icia) .~picigera (112), Justicia america no, J. allsel
liana, J. elegantllla, J. jlava (112), J. montalla, J. orchioides,
J protracta (2/2), J salviae/olia, J. thymi/olio, 1. lrinervia, J. ven
lricosa, Mirandea grisea, Monechma atherstol1ei, M. australis,
M. ineal/uIII, Monechmo sp. (1/3), Net/racanth"s aji'iclllltls (1/2),
OrthO{aClus lI/onlallus (112, leaves and flowers), Peris/raphe cer
Ill/a, Ph/ogacanthus thyrsiflorus (1/2, root), Rultya ova/a (1/2),
Sallchezia lhinophila (bark), Siphonoglossa ramosa.
-'
•
PLANTALIVILOIDS /1lkaloia Te.rl Resu/ls 5
The alkaloids of AdlUltoda vasica have been reviewed (Jain, lophylllllll sp., Haplan/hlls lIi1gherriellsis, Hcmigmphis e/egolls val'.
1984). Acallthlls iJiCijiJ/iIiS contains bcnzoxazolinc¥2-one; the alka¥ crellala, H. hirta, H latebrosa, Hemigraphis spp. (2), Hellrya
loids of Acallthl/s mollis have been reporled (Wolf ct al., 1985) and (= Telramerillm) Yl1ca/(ll1el/sis, Hygrophila taxi/olia, H salici/olia,
new spennine-type alkaloids have becn isolated from Aphe/alldm /-/ygrophi/a .\jJp. (4), /1. .v)illo.m, Hypoesles jloriblllldll, H p/I(llop~
piJosa (Tawil el aI., 1989). In vie}v of the native use of at least one soides, I-/. pUI'plll'ea, !sag/ossa grall/ii, isog/o::"sa !J1)., I. stipitata,
species of Justicia as a hallucinogcn jn South Amcrica (Schultes and I. woodi;, Jacobillia (== Justicia) aschellbomimw, J. candicans,
Holmstcdt, 1968), the report of its presumed content of Ilyptamine J. heterophylla, 1. iIlC(lIU1, 1. mexicalla, J. pal/icil/ala, J. sellow;wUl,
needs corroboration. In this cOIUleetion, the several listed alkaloid Jacobillia spp. (2), J. stellata, Juslicia al1gal/oides, J. belollica,
positive species from other pariS of the world should be of interest. J. belol1icoides, J. beyrichii, J. bmsilialla, J. campeciJialla, J. calll
Negative tests were obtained from the following species: AcolI
py/ostemoll, J. cheirial/tllijolia, J.jiII'Caia, J. gel1dal'llssa, 1. kirkialla,
tllOpsis cardlli/olia, A canthlls ebracteatu.~·, A. 1II0/lis, AdelloslI/a g/u¥ J. kraussii, J. mexic(lIw, J. odorala, 1. ova/a, J. pelio/aris, J. pro
tinosum, Adhatoda sp., Allcy/acallilms baillesii, Allisacalltlms gOIl
cllmbells, J. secllnda, Jus/icia spp. (5), Lepidagalltis /ormosensis,
zalezii, A. qlladrifolills, A. ocholerenae, A. lllllrheri, A. lulellsis,
L. illclIrva, L. microchilo, L. persimilis, Lepidagathis sp., Mackaya
A. wrightii, Anisolesji)/'II/osissiI1lIIS, Aphe/alldm auriontiaca, A. blal/
bella, Macronmgia /ormosissima, Mel/dOl/cia coccinea, M. hoJJ~
cherial/a, A. clWlllissol1ialla, A. deppeana, A. ifl(:erta, A. pilosa,
mOllllseggitllla, M. sefiowiww, Mel/dOl/cia sp. (this gellus is some
Alplle/antll'll ::'1)., ASleracalltha (== Hygrophila) spinosa, Asystasia
times placed in a family of its own, Mendonciaceac), MOllee/llna
gallgelica, A. schimperi, A. varia, Baderia a/bostellala, 8. cristata,
debile, M. divarica/lIlIl, M.jimhricatum, M. lIIo/issiuIII, M. pselldo
B. cros.wlIIdrijormis, 8. discolor, 8. e/egans, 8. guemii, B. herero
palululII, M. scabridlllll, Monechma spp. (2), Odolltollema ca/ysta
triclm, B. kirkii, B. lwu:ijulill, B. /ugal'dii, B. mical/s, B. vbtllsa,
chum, 0. cilspidatulll, Odolltol/ema spp. (2), Pachyslaeliys cocci
B. pl'elorieflsl:5. B. priol/Uoides, B. pUllgell.l', IJ. pyramidata, IJ. rall
dii, B. rigida, B. 'scandens, Barleria sp., Beloperol/e (== Jilsticia) Ilea, Pe"i.~·/rop"e bica/yclI/a((l, P. grandibrachiat(J, P. lIata/ellsis,
PelalidiuIII wvmariculI1, P. barlerioides, P. braeleollllll, P. oblongi
ca/i/ornica, B. comasa, B./ragilis, B. gllt/ata, Be/operolle .\p., Ble
[oliulII, P. /'ubescells, PIU/u/apsis belollica, P. imbricato, Ph/oga
chum nipPolI/CIIIII, B. plagiogy/'ijIorus, BlechuIII ::.p., B/epIUl/'is Cll
pellsis, B. diw:/'sispilla, B. gllllllacea, B. maderaspatellsis, B/epharis canlhtls Ihyrsijlorus, Pselldel'lllltiJemulII praecox, Pseuderal1the
sp., 8. squarrosa, Bravaisia illlegerrillla, Cal'iowrightia g/abrata, mum spp. (2), i?hillacollflius xerophi/us, Rllel/ja alba, R. a/bicoillis,
C. glandu/osa, C. selpyJ/i/olia, Cal'iowrighlia spp. (2), C"aetacan R. a/bijlora, R. bourgei, R. c% rata, R. cordala, R. /orlllosa,
,hus seliger, Chae/ollly/ax hatschbachii, ChilenwthemulI/ vio/a R. ill/lIlda/a, R. macropilyl/a, N. I/Iulijlora, R. lIudifiora val'. yuca/a-
celllll, Codol/acant/llIs pal/eijloms, Crabbell allgLlstifolia, C. hirsula, 110, R. palmeri, R. patu/a, R. pellinslI/aris, R. pi/osa, R. prostrata,
Crossal/dra greellsfockii, C. ulldululae/olia, Cyrtal/lhera pohlialla, Rllellia spp. (4), R. speciosa, R. tubero.m, R. tweet/ialla, Rlmgia
Daedalacallihus (= Erallihemum) I1lOlIfallu.\·, D. lIerVOSlIS, D. pur parvijlora, Rl/spolia hypocralel'ijol'lIIi.<:, Sallchezia I/obilis, Sclero
purescens, Dialllhera (= J/I:)·ticia) ovala, Diapedilllll (= Diclipfera) chilOl/ harveyalllls, Sel'icographis (== JU'<:ficia) cordifolia, Sipl/ofI(}~
assurgel1s, D. chillellsis, D. lIIicral/lhllS, D. I/obilis, D. pedullcula glossa pilosella, S. Iubu/o:w, Slellalldrillm ba/'bawlII, S/1Vbi/alllhes
ris, D. pringlel, D. resupil/ata, D. rigidissima, Disperma (== Duos cllsia, S./ormosallus, Teliostocliya (= Lepidagathis) alopecuroides,
penna) crena/lilli, Dysc/lOriste declIlIlbells, D. fischeri, D. ovala, 7etramer;UIII aure/ill/, T. lIi::'1);dlllll, 7: su/'elllll, Thllllbergia all/oena,
D. microphylla, D. quadrangularis, D. rogersii, DyscilOriste sp., T. atriplici/olia, T. el'(~cl{J, T...ji'agr(llls, 'J: gmlldijIora, T. /anci/olia,
D. verticil/aris, Ebermaiera (= Staltrogylle) cOl'1liclilata, Echo/ill//! T lIota/ellsis, 'l1l11l1belgia sp. (the genus is sometimes placed in
(Jlllplexicallle, E. lilllwealfllll, E. revo/Ilf11I11, mytraria bromoides,
Thunbergiaceae), Thyrsacallllllls (= Odolttonellla) callistaL'hyu.~,
Enm/helllfllll eidomdo, E. lIel'l'OSIIIII, GrapfopllyllwlI piC/lilli, Grap- Tricallthera gigolltell.