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PHYTOCHB}ÍTCAL I}WBSTIG¡,TION OF TRITICALE EJìGOT by RICHATD PETER I4OSZYNSIfl 0ctober 1971 A Thesis Presented to Lhe Faeulty of Graduate Studies UniversitY of ì'fanitoba In Partial Fulfillment of the Requi-rernents for the Degree llaster of Science in Pharmacy ACKNOI\ILEDGEMENTS The author wishes No express his sincere appreciaLion Lo the follovrings Dr. R.C.S" Audette for his supervisionu encouragement, and patience during the course of this sludy; Dr' J' Templeton for his friendly assistanceo his colleagues in the Faculty of Pharmacy at the University of }fanitoba for many useful discussions; trliss Rosella Enns for Ìrer technieal assisLance; and }fr" A1 Arnott of Darlingford, .Ìdanitoba for the supply of Triticale ergot (Rosner cultivar) ' The author also gratefull)'aelnnowledges the receipt of the CanadÍan Foundatíon for the Advaneement of Pharmacy Graduate Students Fellor^¡ship (ffZO)u Nhe fi,naneial assistance provicled by Dr' R"C" l4cÏnnis and the DeparLnent of Plant Science at the university of Ì'lanitobau and the teaching assistantship provided by the Faculty of Pharrnacy at the University of I'fa'nitoba" ABSTRACT PIITTOCHE}{ICAL INVESTIGATION OF TRITICAIÐ ERGOT by RICHARD PETER MOSZYNShT Ergot g,)i.o'rit1 on lritieale grain (Rosner eultivar) v¡as ín¡,'estiga+.ed w.íLh regard to morphologieal characterisLícsu fat eonLent and alk"aloj-d eonterrt (quan'bitative a.nd o,uatitative)" Soxhlet extraction of the porvdered. ergot sample using petroleum ether yiel-ded 16,74% v/w of ergot oil" The total alkaloid content of the sampl€ tfås detennined by a colorimetric assay procedure to be 0'181%' The rrrater-soluble and rqater-insoluble alkaloids constituLed 2A/" and 8Aà of total alkaloids respectively. The ergot alkaloids extraebed from the sample Ïrere separa.ted on a tartaric acid Ímpregnated cellulose column into the peptide alka.loid fractionu the clavine alkaloid fraetÍon and ergometrine" Subsequent thin-la},er chromatography and paper chrornatography of these fraetions identified. ergotamine, the ergotoxine groupe ergometrine, a trace of ergometrinine, penniclavine, setoclaviue, elymoclavine, agroclavine and possibly isopennielavine" The alkaloi-ds from tr,¡o of the cellulose column fractions trere purified and characterized. The melting points, Í:nfra'red, nuclear magnetic resonanceu and nass spectra of the isolated alkaloicis v¡ere recorded" The all<aloid.s lt'ere id-enlified as ergotanine and ergometrirren TABLE OF CONTENT r_l-r Page TNTRODUCTIO[] Claviceps Purpurea I Alkaloids of qlavlqS:ge PuIPure+ I Peptide Alkaloids 3 Clavine A1kaloids I Tbiticale I3 Triticale Ergot L6 ffiPERT}MNTAL 18 T. I'ÍATEMALS Solvents 18 Chemicals 18 Adsorbents I9 fnstruments 19 EquiPment 20 II. I{ORPHOT¡GICAI ÐIA],rINATION 2L 23 III. FAT ASSAY Results and Discussion 23 28 IV" AI,KALOTDAI, ASSAY Results and Discussion 3L VU COITÌ'ÍN CHROI,IATOGRAPTIY 3l+ Results and Discussion )o VI. ÎHIN_LÂITR CHROJ{ATOGRAPIIY 40 FreParation of Adsorbents 40 Preparation of van Urk Spray Reagent l+I 1V Pn oø Basic TLC of Colu¡rn FractÍons 41 TLC of Fraction B U+ l+7 TLC of Fraction C GLC of Fraction C 5L TLC of Fraction E 48 fLC of Fraction I 5L WT. PAPER CHRO]"IATOGRA?HY 53 For"namid.e /øenzene fPetroleum Ether System 53 Fonnamide /nenzene fPyridine Systern 5l+ i[IT.PURIFICATIONOFTSOL¡.TEDERGOTAJ,I{ALOIDS 56 Fraction B (Ergota¡'rine) 56 Fraetion I (Ergornetrine) 56 IX'CHARAOTERIZATIONOFISOLATBDBRGOTALK¿IOIDS 58 Melting Point Determination 58 J¡frared Spectra 59 Nuclear l''lagnetic Resonance Spectra 62 l{ass Spectra 67 v IIST OF TABLES PAGE Iu Tþes of Peptide Alkaloids b 2, Chemical and Physical Characteristics of Peptide Alkaloids , 6 3, Solubilities and l'[elting Points of Peptide Alkaloids 7 l+, Chemical and Fhysical Characteristics of Clavine Alkaloids L0 5" Solubilities and I'felting Points of Clavine Alkaloids 11 6. Results of Fat AssaYs 2l+ Fat Content of Ergot Samples 7 " Comparison of from Various Hosts and Locations 25 8" Characteristics of Ergot Oil 26 g" ComparÍson of Ergot, Oil Fatty Acid Compositd-on 27 10" Cornparíson of Alkaloid Content of Ergot on Different Hosts and fron Different Locaùions 32 11, Fractions Collected from Cellulose Colwm 38 L2, Fraetions conbined from lartaric Acid Impregnated Cellulose Column 4Z L3, R, x 1OO Values of Ergot Alkaloids in t'tethanol/Chloroforn on Silica GeI GF h5 Il+" TLC Results of Fraci;ion B Obtained from Cellul-ose Cotumn b6 v] PAGE L5, TLC Results of Fraction C Obtained from Cellulose Column l+7 16" fLC Results of Fraction E Obtained fron Ce]-lulose Column l+9 ].7, TLC Results of Fraction I Obtained from Cellulose Co1umn 52 18, Meltj¡e Points of Isolated lllkaloids 58 val LTST OF FTGURES PAGB 1, Structure of Ergoli¡e 3 2n Stmcture of d-Lysergic Acid ) 3" Structure of d-Isolysergic Acid 3 4. General Structure of Peptide A1kaloids 5 5. Structure of Ergotmerine I 6" General Stmcture of Clavine Alkaloids I 7" UuV" Spectrum of Ergot Alkaloids 1t 8" Procedure for AJ-kal-oid Assay 3O 9u Development of Column 35 10, Elution of Alkaloids from Cellulose Column 37 11, Basic TLC of Column Fractions l+3 1*2. Paper Chron:atography of Clarrine Alkaloids 55 Lj" IR Spectrum of Ergotan,ine 6o 14" IR Spectrum of Fraction B 6o l-5" IR Spectrum of Ergometrine l'hleate 61 16" IR Spectrum of Fraction I 6L L7 " NÌ4R Spectrum of Fraction I 63 18" Nì4R Spectrum of Ergonetrine þfaleate 6l+ 19, Nl'fiì Spectrum of Fraetion B 65 20, Nl'fR Spectrum of Ergotarnine 66 2L" lrtass Spectrrrm of Ergometrine l4aleate 69 22" }4ass Spectnrm of Fraction I 7O 23" lt{ass Spectrun of Ergotamine 7I 2k, ltfass Spectrum of Fraction B 72 25, Decomposition Sequence of llrgornet,rine ?3 INTRODUCTIOÀT -1- ClavicepsJurpurea Claviceps purpu{ea (Fries) Ti:lasne (famS-fy H¡rpocreaceae, Class Asconycetes) is a parasitic fungus eommonly occurrlng on grasses and cr-rlti: vaLecl eerealsn Ergot of commerce is defined as the drled sclerotiumt or resting stage of Clavieeps Þl¡Ipurea - a hard, purplish, somewhat curved bodyu the size of which is usually cleternined by the size of the grain it parasitizes (1). The generie name Claviceps refers to the club-like charaet,er of the sclerot,iun, purpJ¡.rqa to its purple color (2)" orÍginalIy, the main sources of supply for ergot were spainu Russia and the Bal-kan countries; horrever, Russia and the Balkans export very litt]e ergot today, Currentlyu eonsiderable ergot is being cultivated in Czechoslovakia, Germany, Hungary and Switzertand (2)' other species of clavicqpg are eapable of producing ergots in the ovaries of many other members of the Granrineae fanily sueh as Triticumu Avena, Festuea, Lolium, l'Íolinia ancl Nardus (3 ), A1ka1o1 since galenical preparations of the crude drug are seldont employed in pharmacy in this countr¡r, ergot has been omitted from the offfcial compendia" Neverthelessu the ergot alkaloÍds conLinue to enJoy r,ridespread use as extremely important medieinal agents (2). t"lore than a score of alkaloids have been isolated from the fungUs , -2- Clavicep_s pul-pul:eae growing as a parasiLe on various members of the G::amineae (grasses) family, the nost important of r','ìrich are ergometri-ne, ergotarnine, an¿ a mixLure of ergocornine, ergocri-stine, and ergocryptine (6)" The average content of total alkaloids in the sclero{,ia vari-es between O.OZ5 and. O"t+% but the all<aloid content of individual sclerotia ís also variable; some sclerotia containj-ng very little all<aloidu whÍIe others may contain as much as y/, ß)" The qualitative and quantitative composition of the alkaloids obtained fi'om different hosb plants or grown in saprophytic culture is influenced by a nu¡nber of factors but especially by the iclentíty of the strain of the organism involved (2)" Both peptide alkaloids and nonpeptide (r^,ater-soluble) al-kal-oids were obtained. from parasitically developed ergot selerotia, l,''irile only the r¿ater-solubre tlpe was produced commereiall¡' in saprophytic culture" In 1969u however, l¡rici e! gI, (å.) succeedecl in isola.ting three sLrains of Clavicepq_ pqqruleQ. from selerotia groi,¡fi on rye r'ùich produced, under" subrnerged saprophyt,ic conditionsu ergocr¡ptíne and ergotamine, ergocornine and ergosineu and ergoeristine, respeetively' Large seale production of lysergic aeicì derivatives in submerged culture was achieved in 1960 by Tonolo, Chain and co*i,¡orkers in Italy (Z)" These inves'bigators ul,ilizecl a st,rain of. kl¡æÈg._p*È*slgÀ! i+ìrich procìuced severa.l simple lysergie acid derivatives (2). The ergot alkaloids belong 1,o 'r,he large" significant class of the indole all<aloids and posses$ a teLracycl-ic ring sysLen named ergoline (pígure t) " AIl of the ergot alkal-oids possess this chai"acierisLic base s|ructure (5), -3- 7 D óñ r0 H 5 H HN I Figqle]. Ergoline The natural ergot alkaloids ean be classified into trqc main groups according to their basic chenrical structure; the peptide alkaloidsu and the clavine alkaloids (5)" Tre peptíde or v,ater-insoluble aIl<aloidse are derivatives of d-lysergic acid (figure Z)" Since this compound j.s readily converted to its isomer, d-isolysergic acid (¡'igure 3), corresponding isol¡'sergic N-CH3 d:IqoLys-ergiq.rLc-id Ei gug!" d-LyserBi" Auiu Eieufg 3. -l+ - acid derivatives often acconpany the d-lysergic acid alkaloids in the natural material or are produced during the course of extraction" These peptide alkaloids are aeid amide derivatives of the basic d-lysergic or d-isolysergie structure and consequently yieId, on alkaline hydrolysis, d-lysergic or d-isolysergic acid, The individual alkaloids in this group differ only in the
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  • Ergometrine Maleate

    Ergometrine Maleate

    The European Agency for the Evaluation of Medicinal Products Veterinary Medicines Evaluation Unit EMEA/MRL/237/97-FINAL June 1999 COMMITTEE FOR VETERINARY MEDICINAL PRODUCTS ERGOMETRINE MALEATE SUMMARY REPORT 1. Ergometrine is a naturally occurring alkaloid found in ergot (Claviceps purpurea). It is classified as a water-soluble lysergic acid derivative, and is an orally-active stimulant of uterine contractions. The maleate salt (ergometrine maleate) exhibits greater stability than the free base and is the usual form in which the alkaloid is used in medicinal products. It is used in veterinary medicine in the control of postpartum uterine haemorrhage, removal of fluid from atonic uteri, to prevent pro-lapsed uteri, and judiciously in terms of timing to aid in suturing the uterus after caesarean section or in replacing an everted uterus. Dose regimens are: cows and mares: 2 to 5 mg/animal (intravenously or intramuscularly); ewes, goats and sows: 0.5 to 1 mg/animal (intramuscularly). In human medicine, it is used orally and parenterally in the prevention and treatment of postpartum haemorrhage caused by uterine atony and for the stimulation of uterine involution. Usual oral doses are 500 µg 3 times daily up to 1.8 mg daily (approximately 0.03 mg/kg bw). Ergot alkaloids have been reported to be present in flour from rye, wheat and barley in amounts ranging from 0.01 to 2.36 mg/kg flour. EU legislation restricts the maximum percentage of ergot tolerated in flour to 0.1%. Total daily human intake of ergot alkaloids from contaminated foodstuffs of plant origin has been estimated as up to 7.8 µg/person.
  • Biosynthetic Studies on Ergot Alkaloids and Related Indoles*

    Biosynthetic Studies on Ergot Alkaloids and Related Indoles*

    Acla Phartti. Suecica 3, 71 (1966) Biosynthetic studies on ergot alkaloids and related indoles* STiG AGURELL Department of Pharmacognosy, Kungl. Formaceuiislea Instituiei, Stockholm In this survey, the following papers will be discussed and will be referred to by the Roman numerals given in the following list. I. S.Agurcll and E. Ramstad. Analysis of claviric alkaloids of Penniselum ergot. Lloydia 25,67 (1962) II. S. Agurcll. Thin-layer chromatographic and thin-layer electrophoretic analysis of ergot alkaloids. Relations between structure, R" value and electrophoretic mobility in the clavine series. ltcla Pliarm, Suecica 2, 357 (1965) III. S. Agurell and E.Ramstad. Biogenetic interrelationships of ergot alka- loids. Tetrahedron Letters 501 (1961) IV. S. Agurell and E. Ramstad. Biogenetic interrelationships of ergot alka- loids. Arch. Biocliem, Bioplujs. 98, 457 (1962) V. S. Agurell and E. Ramstad. A new ergot alkaloid from Mexican maize ergot. Acta Pliartn, Suecica 2, 231 (1965) VI. S. AgurelJ. Costaclavine from Penicillium chermesinutn, Bxperieniia 20, 25 (1964) VII. S. Agurell. Isol ysergol from saprophytic cultures of ergot. Acta Pliartn, Suecica 3,7 (1966) VIII. S. Agurell and IVI. Johansson. Clavine alkalo ids as precursors of peptide- type ergot alkaloids. Acta Chern. Scand. 18, 2285 (1964) * Inaugural dissertation. 71 IX.S. Agurell.Biosynthesis of ergot alkaloids in C. paspali, Part I. Incor- poration of DL-4-dimethylallyltryptophan-HC. _4cla Pliarm, Suecica 3, 11 (1966) X. S. Agurell. Biosynthesis of ergot alkaloids in C. paspali. Part II. Incor- poration of labelled agroclavine, clymoclavinc, lysergic acid and lysergic acid methyl ester. Acla Pliarm, Suecica 3, 23 (1966) XI. S.Agurell.