Naming Alkaloids

Most compounds end in ……ine. Majority of alkaloids known by a trivial name. • Colchicine Named after the common name of the organism.

HO O HN O

N H

O

O N H

ergotamine (Claviceps purpurea) also known as the fungus, ergot

N H

Species of organism
COOMe N OCOPh

cocaine (Erythroxylum coca)

Genus of organism
N O O Ph CH2OH

atropine (Atropa belladonna) Deadly nightshade

Physiological effect MeO MeO N H H MeN H OMe OMe emetine (Cephaelis ipecacuanha) Ipecacuanha emesis inducer Mythology HO O N HO morphine (Papaver somniferum) Opium poppy name derived from Greek God morpheus Researcher nicotine (Nicotiana tabacum) named after the researcher Jaen Nicot H N N .

Animal Alkaloids H N N CH2OH O (−)-castoramine (Castor fiberi) Canadian beaver (R)-(+)-muscopyridine (Moschus moschiferus) Musk deer NH OH histrinocotoxin (Dendrobates histrionicus) South American poison dart frog spiro piperidine H HN O H H H OH samandarine (Salamandra maculosa) European fire salamander Cl N HN epabitidine (Epipedobates tricolor) Ecuadorian poison frog .

12. 14 Solenopsis invicta) Southern fire ant precoccinelline coccinelline pyrazine (Coccinella septempunctata) European 7-spotted ladybird beetle O O N N N danaidone (Danaus chrysippus) African Monarch butterfly phermone glomerine European millipede (Glomeris marginata) quinazolone O O O NH O O O NH epilachnene (Epilachna varivestis) Mexican bean beetle azamacrolide N H (Subcoccinella 24-punctata) 24-spotted ladybird .Insect Alkaloids H N N H (CH2)nCH3 H H H H N O H N N OMe 2.6-dialkylpiperidines n = 10.

) Japanese puffer fish (liver and ovaries) .) ascadian (sea squirt) OMe N H N N H OH OH Br Br N Br O N H convolutamine D (Amathia convoluta) bryozoan (moss animal) Manzamine F (Pellina sp.Marine Alkaloids O N Br NH2 N H H2N S S S MeO OMe S S S Eudistomin L (Eudistoma gilboverde) varacin (Polycitors sp.) Okinawan sponge) O O H2N HO H OH O O HN HO OH CH2OH tetrodotoxin (Tetraodon sp.

) animal toxin causes pithomycotoxicosis O OH H HN O O O OH H NH H N OH N H cytochalasin b (Helminthosporia sp.) teleocidin B4 (Streptomyces blastmyceticum) indole alkaloid tumor promotor .Fungal Alkaloids H N O O O N COOH OH NHCH3 HN fusaric acid (Fusarium heterosporium) mycotoxin viridicatin (Penicillium viridactum) 2-quinolone chief mold on stored corn rugulovasine A (Penicillium concavo-rugulosum) Cl MeO HO HO O S N N S H O N OMe sporidesmin A (Pithomyces chartarum.

Me H H Me O Me N H Me OH H O H OH Me (−)-penitrem D (Penicillium crustosum) tremogenic mycotoxin O NH N N H O HN N roquefortine (Penicillium roquefortii) blue cheese HO HOOC H NMe H O HN O H N H N H N O NMe H O D-(+)-lysergic acid N H ergotamine (Claviceps purpurea) sclerotium of fungus develops on the ovary of rye. Secale cerale .

Bacterial Alkaloids Very rare in nature. O N procyanine (Pseudomonas aeroginosa) deep blue colour .

Alkaloids must be free from impurities and artefacts. H2SO4. petroleum ether). Crude material must be defatted (hexane. Extract crude alkaloid from raw material into suitable solvent. gums. starches Organic solvent soluble impurities . saponins.Alkaloid Extraction and Isolation General aspects Small amounts of alkaloid to isolate. Purify alkaloid by repeated conversion from base to salt and partitioning between organic and aqueous phases. dichloromethane) • Diethylether • Ethylacetate Groups of Impurities to be Removed H2O/Ethanol soluble impurities • proteins. tartaric acid Solvents • Benzene • Toluene • Chlorinated solvents (chloroform. Alkalis • NH3/NH4OH • Ca(OH)2 Acids • HCl.

waxes. tartaric acid Steam distilaltion • nicotine pH gradient separation • Vincristine. fats. resins. H2SO4.• Lipids. pigments Organic Acids • NH4OH Organic bases other than alkaloids • Selective solubilities • Ion exchange resins • Preparative HPLC • Thick layer (preparative) TLC • Flash column chromatography Extraction Methods Kian-Douglas method • NH3/NH4OH Stats-Otto method • HCl. vinblastine (Catharanthus roseus) .

40. UV. 4765-4773 Fenical W.Structural Elucidation Mass spectrometry • FAB (Fast Atom Bombardment) • EI (Electron Impact) • MALDI-TOF (Matrix Assisted Laser Desorption/Ionisation – Time of Flight) NMR (Nuclear Magnetic Resonance) • 1-D: 1H. 1991) Harran P. elemental analysis X-ray crystallography Total synthesis Total synthesis – ultimate proof of structure HO O H N HN O O N N O Cl H2N Cl NH O H N HN O O N N O Cl Cl NH HO O NH OH O (−)-diazonamide A (revised structure. Soc. HMBC. Int. 13C.. 1991. 2001) (−)-diazonamide A (proposed initial structure. J. Chem. Angew. TOCSY. 2001. Chem. et al. Ed. NOE Derivitisation Degradation studies IR. Am. 113.. 15N • 2-D: HMQC. et al. 2303-2304 .G.

E. 9008-9009 . J. C-NMR.. Am. 2002. Chem.(–)-Diazonamide A (toxin extracted from the marine invertebrate Diazona angulata). Quadrigemine C Psychotria colorata Amazonian plant used for treating pain tetrapyrrolindoline alkaloid Overman L. et al. Total synthesis – ultimate proof of absolute configuration (–)-Quadrigemine C (representative of methyltryptamine derived plant alkaloid). H. HRMS. Soc. 124. HPLC properties identical to natural product. H H Me N N H H Me N N a higher order N- absolute stereochemistry established as R (1999) N N H H Me N N H H Me total synthesis (2002) ultimately determined absolute stereochemistry of the vicinal quaternary carbons. 1 13 Optical rotation.

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