Main description:

During the past three decades the organic chemist has become in creasingly used to take advantage of more and more complex instrumenta tion and physical measurements in lieu of laborious, time-consuming and often ambiguous chemical transformations. Mass spectrometry is perhaps the most recent, most complex and most expensive addition to this field. In view of the astonishingly quick acceptance of nuclear magnetic reso nance by the organic chemist it is, in retrospect, surprising that he has neglected mass spectrometry for such a long time. This can be explained, in part, by the complexity of the instrumentation and some technical shortcomings of the earlier commercially available instruments but, to an even greater extent, it reflects also the prejudices against a technique that was originally mainly used for quantitative gas analysis. The usefulness of mass spectrometry as a qualitative technique in organic chemistry rather than a tool for quantitative analysis was more and more recognized towards the end of the last decade. A rather spectacular development followed during the intervening few years to the point that now any reasonably well equipped modern organic laboratory is supplied with, or at least has access to, one or more mass spectrometers suitable for work on organic compounds. Within the realm of organic chemistry the technique has become much more important, if not indispensable, for the natural products chemist while its application to synthetic problems is much less pro nounced.

Contents:

- Table des matieres.- Mass Spectrometry of Selected Natural Products.- I. Introduction.- Instrumentation.- Principles of the Interpretation of Mass Spectra.- II. Indole Alkaloids.- 1. Correlation of Closely Related Alkaloids.- Correlation of the Carbon Skeleton.- 2. Dihydroindole Derivatives.- Aspidospermine Skeleton.- Vincadifformine.- Akuammicine and Condylocarpine.- Ajmaline.- 3. Indole Derivatives.- Sarpagine.- Eburnamine.- Yohimbines.- Oxindoles and Pseudoindoxyls.- 4. 'Dimeric' Indole Alkaloids.- Voacamine.- Vinblastine.- Pleiomutine.- Villalstonine.- III. Tetrahydroisoquinoline Alkaloids.- Aporphine Alkaloids.- Xylopine.- Protopine.- Papaver Alkaloids.- IV. Bisbenzyl-tetrahydroisoquinoline Alkaloids.- V. Polycyclic Tetrahydroisoquinoline Alkaloids.- Amaryllidaceae Alkaloids.- Morphine.- VI. Miscellaneous Alkaloids and Other Nitrogen Containing Natural Products.- VII. Quarternary Bases.- VIII. Natural Products Other than Alkaloids.- Lipids.- Steroids.- Carbohydrate Derivatives.- Nucleosides.- Amino Acid Sequence in Oligopeptides.- IX. High Resolution Mass Spectrometry.- Element Map.- Computer Interpretation.- References.- Pflanzliche Steroide mit 21 Kohlenstoffatomen.- I. Einleitung.- II. N-freie Pregnanderivate aus Scrophulariaceen.- Die Struktur der einzelnen Aglykone.- a. Diginigenin.- b. Digifologenin.- c. Digipurpurogenin.- d. Digiprogenin.- e. Purpnigenin.- f. PurDrogenin.- g. Digacetigenin.- III. N-freie Pregnanderivate der Asclepiadaceen.- Die Struktur der einzelnen Aglykone.- a. Pregnenolon und Allopregnanolon.- b. Weitere Aglykone ohne OH an C(8): Benzoylramanon, Pergularin, Utendin, Tomentogenin 108.- c. Aglvkone mit OH an C(8) Cynanchogenin, Lineolon, Sarcostin, Penupogenin, Tayloron, Metaplexigenin 109.- d. Aglykone mit einer Glykolgruppierung an C(11) und C(12): Drevogenine A, B, D und P, Kondurangogenin A.- IV. N-freie Pregnanderivate aus Apocynaceen.- a. Progesteron.- b. Holadyson.- c. Ketone aus Paravallaris microphylla.- V. N-haltige Pregnanderivate aus Apocynaceen.- a. An C(3) aminierte Derivate, OH an C(20): Funtumidin, Holadysamin, Holaphyllidin.- b. An C(3) aminierte Derivate, Ketogruppe C(20), 5?: Funtumin, Holamin, Holaphyllamin, Holaphyllin.- c. An C(?) aminierte Derivate mit weiteren O-Funktionen im Molekul bzw. keine an C(20), Holadysin, Kurchilin, Kurchiphyllin, Kurchiphyllamin.- d. Paravallarin-Typ (Lactonring E), ?5: Paravallarin, Paravallaridin, Kibatalin.- e. Nur an C(20) aminierte Derivate, 5?: Funtuphyllamine A, ?, C, Funtumafrine ? und C, Holafebrin, Conopharyngin, Irehamin, Irehin (= Buxomegin), Terminalin.- f. An C(3) und C(20) aminierte Derivate: Chonemorphin, Malouetin, Epipachysamine A (= Saracodin), ?, C (Dictyodiammj, D, E und F, Pachysamine A und B, N-Methylpachysamin A 119.- g. An C(3) und C(20) aminierte Derivate, 5? und weitere O-Funktionen im Molekul: Malouphyllin, Pachysandrine A, ?, C und D, Basen XI und XIII aus P. terminalis, O-Desacyl-pachysandrin ?.- h. An C(3) und C(20) aminierte Derivate und ?5: Irehdiamine A und B, Kurchessin (= Saracodinin ?), Saracoccin (= Saracocin), 3? 20 S-Bisdimethylamino-?5-pregnen.- i. An C(3) und C(20) aminierte Derivate mit einer OH-Gruppe an C(18), ?5: Holarrhimin, Monomethylholarrhimine I und II, Tetramethylholarrhimin, Holarrhidin.- j. Conessin-derivate mit O-Funktionen an C(3) bzw. C(7), ?5: Latifolin, Norlatifolin, Latifolinin, Funtulin, Funtudienin, Holonamin.- k. Conanin-derivate mit N-Funktion an C(3), 5?: Malouphyllamin, Dihydro-conessin, Dihydro-conessimin, Dihydro-conkuressin, Funtessin.- 1. Conenin-derivate mit N-Funktion an C(3), ?5 Conarrhimin, Conamin, Conessimin, Conimin, Isoconessimin, Conessin, 7?-Hydroxyconessin, 12 ?-Hydroxyconessin, Holafrin, Holarrhenin, Holarrhetin.- m. Conanin-derivate mit Doppelbindungen ?5,18: Conkurchin (= Irehlin), Conessidin.- n. Kurcholessin.- ?. D-Homo-androstan-Alkaloide: Dictyolucidin, Dictyolucidamin.- VI. Pregnenolon als biogenetische Vorstufe fur Digitanole, Cardenolide, Bufadienolide und Aminopregnan-derivate.- Cyelite: Biosynthese, Stoffwechsel und Vorkommen.- I. Einleitung.- II. Nomenklatur der Cyclite.- A. Schreibweise der Formeln.- B. Bezifferung der Ringkohlenstoffatome.- C. Benennung der Verbindungen.- D. Bezifferung der optisch aktiven Cyclite; Richtungssinn der Bezifferung.- III. Biosynthese.- A. Biosynthese des myo-Inosits.- 1. Vorversuche.- 2. Versuche mit selektiv markierten Vorstufen.- a. Fruhe Untersuchungen uber die Entstehung von myo-Inosit in Mikroorganismen.- b. Untersuchungen uber die Entstehung von myo-Inosit aus D-Glucose in hoeheren Pflanzen.- ?. Untersuchungen uber die Biosynthese von myo-Inosit aus D-Giucose in Tieren.- d. Neuere Untersuchungen uber die Umwandlung von D-Glucose in myo-Inosit in Mikroorganismen.- e. Untersuchungen uber den Mechanismus der Umwandlung von D-Glucose in myo-Inosit und uber Zwischenprodukte dieser Ringschlussreaktion.- B. Biosynthese der Methylather des myo-Inosits.- C. Biosynthese von Glykosiden des myo-Inosits.- D. Die Herkunft des myo-Inosit-Restes in Phytinsaure und in den Phosphoinsitiden.- E. Bildung von scyllo-Inosit.- F. Bildung von D-chiro-Inosit und D-Pinit.- G. Bildung von L-chiro-Inosit und seiner Methylather.- H. Bildung von L-Quercit, L-Viburnit und L-Leucanthemit.- I. Bildung von Amino-desoxycycliten.- IV. Katabolischer Stoffwechsel.- A. Oxydationsreaktionen unter Erhaltung der Cyclitstruktur.- B. Oxydative Aufspaltung des Cyclohexanringes.- 1. Abbau im tierischen Organismus oder durch Enzympraparate tierischer Herkunft.- 2. Oxydative Aufspaltung durch Mikroorganismen und durch Enzyme mikrobiellen Ursprungs.- 3. Oxydative Aufspaltung in hoeheren Pflanzen.- V. Vorkommen der Cyclite.- A. myo-Inosit.- B. Methylather des myo-Inosits.- C. scyllo-Inosit.- D. D-chiro-Inosit und seine Methylather.- E. L-chiro-Inosit und seine Methylather.- F. DL-chiro-Inosit.- G. Methylather des muco-Inosits.- H. Derivate des neo-Inosits.- I. C-Methylinosite.- J. Cyclohexanpentole und Cyclohexentetrole.- K. Amino-desoxycyclite.- VI. Tabellen.- The Chemistry of the Order Cupressales.- I. Introduction.- II. Botanical Classification of the Order Cupressales.- III. Chemical Constituents of Cupressales.- 1. Cyclitols and Simple Phenols.- 2. Lignans.- 3. Flavonoids and Biflavonyls.- 4. Leaf Waxes and Other Less Investigated Constituents.- 5. Tropolones.- 6. Terpenes.- a. Monoterpenes.- Thujic Acid.- Chamic and Chaminic Acids.- Shonanic Acid.- Other Monoterpene Acids from Calocedrus formosana.- b. Sesquiterpenes.- Nerolidol.- Bisabolanes.- Humulene and Caryophyllene.- Elemanes.- Selinanes.- Eremophilanes.- Cadinanes and Related Terpenes.- Longifolene and Juniperol.- Cedranes.- Thujopsanes.- Widdrol.- Cuparanes.- c. Diterpenes.- Labdanes.- Pimaranes.- Rimuene.- Ferruginol and Related Terpenes.- Totarol and Related Terpenes.- Phyllocladene and Related Tetracyclic Diterpenes.- Verticillol.- d. Triterpenes.- e. Biogenetic Aspects.- IV. Some Chemotaxonomic Aspects.- Phenolic Compounds.- Tropolones.- Terpenes.- General Remarks.- V. Chemical Constituents of Cupressales Species.- VI. Tables.- 1. Distribution of Lignans in Cupressales.- 2. Physical Constants of Lignans from Cupressales.- 3. Distribution of Biflavonyls and Composition of Leaf Waxes in Cupressales.- 4. Physical Constants of Biflavonyls from Cupressales.- 5. Distribution of Tropolones in Cupressales.- 6. Physical Constants of Tropolones from Cupressales.- 7. Distribution of Selinanes, Guaianes and Related Sesquiterpenes in Cupressales.- 8. Distribution of Cadinanes and Related Sesquiterpenes in Cupressales.- 9. Distribution of Sesquiterpenes in Cupressales: Caryophyllane, Humulane, Longifolane, Cedrane, Thujopsane and Cuparane Types.- 10. Physical Constants of Sesquiterpene Hydrocarbons from Cupressales.- 11. Physical Constants of Sesquiterpene Alcohols from Cupressales.- 12. Physical Constants of Sesquiterpene Aldehydes, Ketones and Acids from Cupressales.- 13. Physical Constants and Distribution of Diterpenes in Cupressales.- References.- Quinone Methides in Nature.- I. Introduction.- II. Stable Ouinone Methides in Nature.- 1. Citrinin.- 2. Pulvilloric Acid.- 3. Ascochitine.- 4. Purpurogenone.- 5. Fuscin.- 6. Celastrol and Pnstimerin.- 7. The Perinaphthenone Group.- a. Haemocorin.- b. Atrovenetin and Herqueinone.- c. Biogenesis of Plant and Fungal Perinaphthenones.- 8. Anhydro Bases of the Flavonoid Series.- 9. General Discussion.- a. Structural Features Contributing to Stability.- b. Tautomeric Forms.- c. General Reactions.- III. Quinone Methides as Intermediates in Biochemical Processes.- 1. Oxidative Phosphorylation.- 2. Oxidative Metabolism.- 3. Miscellaneous Processes.- References.- The Pyrrolizidine Alkaloids. II.- I. Introduction: Occurrence and Nature of the Pyrrolizidine Alkaloids.- II. The Free Bases and the Basic Hydrolysis Products.- 1. The Absolute Configurations.- I-Hydroxymethylpyrrolizidines.- 7-Hydroxy-I-hydroxymethyl- pyrrolizidines.- 2. New Bases.- Otonecine.- Loline, Lolinine, Norloline and Fusticine.- 3. Syntheses of the "Necine" Bases.- Pyrrolizidine.- I-Methylpyrrolizidine.- I-Methylene- pyrrolizidine.- 3-Methyl- and 3-Hydroxymethylpyrrolizidines 342.- I-Hydroxymethylpyrrolizidines.- Dihydroxymethyl- pyrrolizidines.- III. The Acids Associated with the Pyrrolizidine Alkaloids.- 1. C10-Adipic Acids and Retusanecic Acid.- Hygrophyllinecic Acid.- Seneciphyllic, Isoseneciphyllic "Spartioidinecic" and Riddellic Acids.- The Acids from, and the Structures of Jacobine, Jacoline and J aconine.- Synthesis of Integerrinecic and Senecic Acids.- The Synthesis of Dihydrosenecic Acid.- Sceleranecic and Sceleratinic Acids.- Sarracinic and Mikanecic Acids.- 2. The Glutaric Acids.- Monocrotalic, Dicrotalic, Fulvinic and Crispatic Acids, and the Acids from Retusine.- Trichodesmic and Junceic Acids.- Grantianic Acid and "Retusaminecic" Acid.- C-Acids: Hydroxylated 2-Methylpentane-3-carboxylic Acids.- Latifolic Acid.- Heliotramide.- IV. The Structure of the Native Alkaloids.- 1. The Alkaloids Containing the C10-Adipic Acids.- Seneciphylline.- Spartioidine.- Ultraviolet and Infrared Spectra in the Study of Geometrical and Stereoisomerism: Seneciphylline, Spartioidine, Senecionine, Integerrimine and Usaramoensine.- Retusamine, Otosenine (Tomentosine), Renardine and Onetine.- General Structures.- Sarracine.- 2. Dicrotaline and the Alkaloids Containing Trimethyl Glutaric Acids.- Spectabiline (Acetyl monocrotaline) 368.- 3. Alkaloids Containing Acids with the 2,3-Dimethyl-4-isopropylglutaric Acid bkeleton.- Trichodesmine, Junceine, Incanine and Grantianine.- 4. Alkaloids Containing Hydroxylated 2-Methylpentane-3-carboxylic Acids.- Echinitine, Echuimine, Echimidine, Heliosupine, Macrotomine and Cynoglossiphine.- Latifoline.- Thesine and Thesinine.- V. Biosynthesis.- Alkaloid Variation in the Plant.- Retronecine.- Senecic and Retronecic Acids.- Combination of Acid and Base.- VI. Pharmacology.- The Hepatotoxic Activity of the Pyrrolizidine Alkaloids.- Mechanism of the Toxic Action.- Possible Other Uses for Fully Saturated Pyrrolizidines.- VII. Tables.- References.- Some Aspects of Virus Chemistry.- I. Introduction.- II. The Chemistry of Viral RNA.- Size, Composition and Conformation.- Nucleotide Sequences and End Groups.- Endoattack.- Exoattack for Identification of End Groups.- Determination of Terminal Sequences.- Stepwise Degradation of RNA.- III. The Chemistry of Viral Protein.- Molecular Size.- Amino Acid Sequence.- Peptide Sequences.- Chain Conformation.- Relation of Viral Infectivity to the Structure and Interaction of its Components.- Modification of Viral RNA and its Consequences.- References.- Namenverzeichnis. Index of Names. Index des Auteurs.- Sachverzeichnis. Index of Subjects. Index des Matieres.