Synthet1sche Chemle der Carot1nolde. Von H. H. INHOFFEN und H. SIEMER, Organisch-chemisches Institut der Technischen Hochschule, Braunschweig

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1 Inhal tsverzeichnis. t j.cont~nts. -T~bl~ des matieres. Synthet1sche Chemle der Carot1nolde. Von H. H. INHOFFEN und H. SIEMER, Organisch-chemisches Institut der Technischen Hochschule, Braunschweig I I. Allgemei1ie Ei1ileitung I Nomenklatur-Vorsch1ag und Ei1iteilung des Stoffes. 2.Zur Stereochemie der Carotinoide 4 Die m6g1ichen Stereoisomeren 6 Spektrale Vera.nderungen durch t1'ans -cis-isomerisierung 8 "cis-peak"-effekt 8 II. Synthesen von C8o- und C81-Kohlenwasserstoffen als Modellsynthesen...9 III. Bis-nor-methyl-p-carotin und 7,7'-Dihydro-p-Caroti1i 13 Bis-nor-methyl-p-caroti1i ; 13 7,7'-Dihydro-p-Caroti1i 16 IV. p-caroti1i-synthesen 19 p-caroti1i-synthesen CI8+C8+CI Caroti1i-Synthese ci8+cl+c1' 22 Stereoisomerisierungvon I5,I5'-mono-cis-p-Caroti1i. 26 p-caroti1i-synthese ~8+C.+CI8...; 27 V. Lycopi1i und el-carotin 28 LyCOpi1i 28 el-caroti1i 30 VI. Synthesen von h6heren Caroti1i-Homologen. 31 I6;If1!.Homo-p-Caroti1i 31 Decapreno-p-caroti1i und Decapreno-el-caroti1i. 34 Dodecapreno-p-Caroti1i 35 JiteraturverzeiChnis JS Synthesis and Properties of Vitamin A and Some Related Compounds. By J. G. BAXTER, Distillation Products Industries. Rochester, New York, 41 Introduction 42 I. Synthesisof Yitami1i A, 43 I. Via Esters of fj-ionylideneacetic Acid 43 Ethyl p-ionylideneacetate and its p",-unsaturated Isomer. 46 p-ionylidene-ethan01 50 CI8-Ketone 50

2 ~ '. - IV inhaltsverzeichnis.. -Contents.. -Table des mati~res. - Vitamin A Acid ethyl ester and its.b;'y-unsaturated.isomer. 50 Vitamin A 5I Isomer of Vitamin A 5I Synthesis by WEND~R, SLATES, TRENNER and TISHLER 5I.B-Ionylideneacetaldehyde Synthesis of Vitamin A via Esters of.b-ionyltdenecrotonic Acid B-Ionylidenecrotonic Acid 53 C18-Ketone 53 Vitamin A Aldehyde 56 Vitamin A Acids. 56 Vitamin A,..., 57 Synthesis by ScHwARZKOPF, CAHNMANN, LEWIS, SWIDINSKY and WUEST Synthesis of Vitamin A via "C14-Aldehyde'.' 58 Cu-Aldehyde 60 AUylic Rearrangement, Synthesis of Vitamin A by Other Methods. 64 ll. Synthesis and Biplogical Activity of Some CompoUnds Related to Vitamin A 66 Alcohols., 66 Estersand Ethers of Vitamin A :.. 74 ~~~:::e~~..::::::::::::::::::::::::::::::::::::::::::::::::::: ;~ Hydrocarbons...'. 77 Vitamin A Acids..~.., 79 Conclusions : 80 III. Relationship between Vitamin A and Carotenes. 80 References. 80 Les Antivitamines. Par P. MEUNIER, Laboratoire de chimie biol()gique de la Faculte des Sciences, Lyon, 88 Introduction. 88 I.Les antagonistes des vitamines hydrosolubles Les antagonistes de la thiamine 90 a) pyrithiamine 90 b) Oxythiamine, 91 c) Homot4iamine-glycol, 9l d) Antagonistes de la thiamine de nature enzymatique: thiaminases diverses 92 e) Antithiamines des f9ug"'res 93 2" Les antagonistes des flavines et de la vitamine B Les antagonistes de l'acide pantothenique 95 4Q Les antagonistes de lapyridoxine 95 a) Activite vitaminique B6 95 b) Constitution thimique des antivitamines B6 96 c) Desoxypyridoxine. 96 d) Methoxypyridoxine 97 e) Autres antivitaminesb Les antagonistes de l'acide nic()tinique 98 I 6 Les antagonistes de la biotin~ 98 7 Les antisulfamides loo

3 ~ ~~ Inhaltsverzeicbnis.- COntents. -Table d~ matieres. V 8cr Les anti-acides f01iques '; L.activite antisu1famide et antisu1fone de derives voisins ~ l.acide p-aminobenzoique :' 101 II. Les antagonistes des vitamines lipos01ubles 102 L. t.. t. I an IVl amme A Les antivitamines E Les antivitamines K 104. Bibliographie 1 7 / Recent,1nvestigations on Ergot Alkaloids. By'A. STOLL, Chemische Fabrik Sandoz. Basle. Switzerland 14 I. Historical Introduction 114 II. The Structure of the Ergot Alkaloids 119 I. Introduction The Structure of Lysergic Acid ; Structure of the Peptide Portion 134 III. The Individual Alkaloids of Ergot, 49 I. Ergobasine and Ergobasinine Ergotamine and Ergotaminine : Ergosine and Ergosinine Alkaloids of the Ergotoxine Group Ergocristine and Ergocristinine Ergokryptine and Ergokryptinine 16I 7. Ergocornine and Ergocorninine 162 IV. Partially Synthetic and Hydrogenated Derivatives of Ergot Alkaloids. 163 I. Partially Synthetic Derivatives of Lysergic Acid The Dihydro Derivatives of the Natural Alkaloids of Ergot. 167 References. 170 Die Alkaloide der Menispermaceae-Pflanzen. Von M. TOMITA, Pharmazeutisches Institut der Universitat Kyoto. 175 I. Einleitung, 17.6 II. Die in Menispermaceae a1ffgefundenen Alkaloide 177 A. Durch RONDO und seine Mitarbeiter untersuchte Pflanzen 177 B. Von nicht-japanischen Forschern untersuchte Pflanzen. 177 C. Pflanzen. in denen vo~ RONDO und MitarbeiterIl das Vorkommen von Alkaloiden festgelegt wurde.,..178 D. In der Literatur als alkaloidhaltig angegebene Pflanzen. 178 E. Aus Rohmaterialien des chinesischen Drogenmarktes isolierte Alkaloide 178 F. Nicht zu den Menispermaceae gehorende, Biscoclaurin-Basen enthaltende Pflanzen : 179 Berberidaceae Anonaceae Magnoliaceae Monimiaceae 179. r:. Tn r,1r"r....nth"lt..n.. R;,."oclaurin-Alkaloide : 179

4 VI Inhaltsverzeichnis. 7- Contents. Table des matieres. lli. Klassifizierung der Menispermaceae-Alkaloide I80 Systematik der :5iscoclaurin-:5asen I80 Gruppe I. :5asen mit einem Athersauerstoff I80 -Gruppe IIa. :5asen mit zwei Athersauerstoffen (Tetrandrin-Typus) I80 Gruppe II b. :5asen mit zwei Athersauerstoffen (IsoChondendrin- Typus) ", I80 Gruppe III a. :5asen mit drei Athersauerstoffen (Dip4enylendioxyd- Typus) Gruppe IIIb. :5asen mit drei Athersauerstoffen (Depsidan-Typus) I80 IV. Allgemeine Untersuchungsprinzipien der :5iscoclaurin-Alkaloide. I8I I. Per~nganat~Oxydation des Alkaloides selbst oder seines HoFMANNschen Abbauproduktes, I81 2. Ozon-Spaltungvon Methinbasen I82 3. Aufspaltung durch Natrium in fltissigem Ammoniak 184 V. Spezieller Teil : 186 I. :5enzylisochin01in-Typus ; I86 Coclaurin Isococlaurin Magnocurarin '- Salicif01inchlorid Phenanthropyridin-Typus 188 Sinomenin Disinomenin Tuduranin Step~anin I89. -Crebanin Phanostenin I90. -Dicentrin I :5erberin-Typus I90 :5erberin I9. -Palmatin I90. -C01umbamin I90. -Jatrorrhizin I90. -Sinactin I9I. ~ 4. :5enzochin01izin-Typus I9I Rotundin I :5iscoclaurin-Typus. 1;92 Gruppe I. Dauricin I92. -Magn01in I92.. -Magn01amin Aztequin I93. Gruppe IIa. :5erbamin I93. -Isotetrandrin I94. -Tetrandrin I94. - Phaeanthin I95. -Cepharanthin I95.. -Oxyacanthin I95. -Repandin I97. -Daphnandrin I98. -Daphn01in (Trilobamin) I98. - Arom01in I98. -Epistephanin I99. -Hypoepistephanin 199. Gruppe IIb..IsoChondodendrin I99. -Cycleanin Protocuridin Neoprotocuridin 20I.. -:5ebeerin20I. -Chondrof01in Tubocurarinch10rid ChondoCUrin 202. Gruppe liia. Trilobin Isotrilobin Menisarin Normenisarin Micranthin 205. Gruppe IIIb. Insularin Strukturell ungekla.rte :5asen Optische Isomerie der :5iscoclaurin-:5asen Charakterisierung der :5isc6claurin-:5asen. 209 VI.. :5iogenetische :5etrachtungen tiber :5iscoclaurin-:5asen 209 VII. Medizinische Anwendungen, 2[3 Literaturverzeichnis..., 214 I80

5 , Inhaltsverzeichnis. -Contents.. ~ Table des matieres. VII Naturally Occurring Coumarins. By F. M. DEAN, The University r of Liverpool. Depa,rtment ot Organic Chemistry. 225 I. General Structural Features : 22Q II. The Chelriistry of the Coumarin System. 229 Conversions and Degradation 229 The Synthesis of Coumarins 235 Theoretical Considerations 237 III. Occurrence, Isolation _~nddetermination 239 Iy, Some Biochemical Properties,,: 24 " V. Simple Coumat:ins, 242 Couma;in Dihydro-coumarin Umbelliferone Het:~iarin Aesculetin244. -Scopoletin Fabiatrin Ayapin Citropten Daphnetin Fraxetin Fraxidin248. -Isofraxidin Fra~ino Eugenin Gerat;1oxy-7-methoxycoumarin Suberosin Z5. - Collinin Brayleyanin 25, -Umbel1iprenin Toddalolactone 251; -Aculeatin Auraptene Ostruthin Osthenol Ostho Ammoresino Dicoumarol 257. VI. Furanocoumarins..,,,, 257 Psoralene260. -Angelicin Bergapten Bergapto Isobergapten Xanthotoxin Xanthotoxo Sphondin Sphondylin Isopimpinel1in Pimpinellin Isoimperat.orin Oxypeucedanin Ostrutho Imperatorin Bergamottin Phellopterin Byakangelicol 27&. --.: Byakangelicin 27. -Ferulin Nodakenetin Ma,rmesin Peucedanin Athamantin 275. VII. Chromeno-lX-pyrones,,, 276 Xanthyletin27i- -Seselin 278: -Xanthoxyletin Luvangetin Al1oxanthoxyletin Braylin 281. VlII.3:4'"Benzc.oumarins 282 2' :3" -Dihydroxydibenz-lX-pyrone : 6: 4' : 6'-Dihydroxydiphenic acid dilactone El1agic acid : 4'~Dihydroxy-6:6'-dimethoxydiphenic acid dilactone 284. References., 285 J The Biosynthesis of Proteins and Peptides, including Isotopic Tracer Studies. By H. BORSOOK, California Institute of Technology. Pasadena, California. 292 I. Introduction. 293 I. The Theory of Endogenous and Exogenous Protein Metabolism The Theory of Protein Metabolism as a Dynamic Steady State a) Indirect Evidence. 294 b) Direct Evidence. : 297 c) Lability of Enzyme Proteins : 298 II. The Measurement of Protein Turnover. 299

6 Ill. Incorporation of Labeled Amino Acids in vivo 300 I. N15-labeled Amino Acids as Tracers 3 O 2. C14- and S85-labeled Amino Acids a~ Tracers. 303 a) In Normal Tissues. 303 b) In Tumors. 3 5 c) Influence of Hormones 305 d) Incorporation ~f Foreign Amino Acids. 308 IV. Incorporation of Labeled Amino Acids in vitro 309 I. Incorporation of Carbon Dioxide into Amino Acids Net Synthesis of Protein in vitro 3I2 3. Comparison of Incorporation 0 AmiI.1o Aci4s: in vivo and in vitro Amino Acid Incorporation in Different Cell Fractions The Nucleus, Amino Acid lncorporation, and the Maintenance of the Amino Acid Pattern in Proteins ; 314 6: Nucleic Acids, Protein Synthesis and Amino Acid Incorporation into Proteins Normal, Foetal and Tumor Tissue, Effect of Concentration of Labeled Amino Acid on its Rate of Incorporation Does Incorporation of One Amino A~id Require the Presence of Others? 316 a) Feeding Experiments 316 b) In viva Experiments with Single Labeled Amino Acids: 316 c) In vitra Experiments with Labeled Amino Acids. 317 V. The Biological Significance of the High Lability of the Proteins in the Cell 319 VI. Mechanism of Peptide Bond Synthesis. : T. Heats and Free Energies of Formation of Some Amino Acids and Peptides (Solids} Free Energies of Forrilation of Some Peptides in Aqueous Solution 320 3; The Effect of PH on the Free Energy Change in Peptide Formation Peptide Synthesis by Proteases and Peptidases. : 322 a) Classification of Enzymatic Peptide Syntheses According to the Sign and Magnitude of the Free Energy Change ( -L1F) 322 b) Peptide Syntheses where -LJF is Positive and Large. 323 c) Peptide Syntheses where -L1Fis Small and the Peptide is Relatively Insoluble. 325 d) Plastein Formation. 327 e) Peptide Synthesis in an Exchange Reaction during Hyd1:9lysis (Transamidation and Transpeptidation). 328 f) Peptide Synthesis from Amino Acid Esters. 333.'j. Glutamo- and Asparto-Transferases Syntheses where -L1F is Negative and Large, Coupled with High Energy Phosphate. 336 a) Synthesis of Glutamine 336 b) Sylithesis of Hippuric Acid : 337 c) Synthesis of p-aminohippuric Acid. 338 d) Synthesis of Ornithuric Acids, 339 e) Synthesis of Glutathione ~4.I

7 ",,,,;;-~-~- Inhaltsverzeichriis;?C6ntent$. ~ 4;;Tabledes matieres, c "- - c VII. Mechanism of Amino Acid Incoryoration ihtoprotein) 343 I. Effect of Inhibiiors Amino Acid 1ncorporation and Phosphorylation Heat-Stable Co-factors for Amino Acid Incorporation Is Amino Acid Incorporation Synthesis of Protein de novo or an Exchange? The Possibility of Peptides as Intermediates in Protein Synthesis The Linkage of Incorporated Amino Acids...: 349 References. 352 The Enzymes of Nucleoside Metabolis~. By HERMAN M. KALCKAR, Cytophysiological Institute of the University, Copenhagen. 363 Introduction. 363 I. The Preparation of Nucleosides 364 II. The Enzymes of Nucleoside Metabolism I. Purine Nucleoside Phosphorylase Pyrimidine Nucleoside Phosphorylase Trans-N-Glycosidase Ribosidase Phosphoribomutase Degradation and Synth~is of Ribose-Phosphoric Esters Nucleoside Deaminases 378 III. Phospho-Ribosides 381 I. Preparation and Properties of Ribose-I-phosphate 38I 2. Enzymatic Synthesis (jfribosides Preparation and Properties of Deoxyribose-I-phosphate Enzymatic Synthesis of Hypoxanthine Deoxyriboside 386 IV. Trans-N-Glycosidic Reactions 387 I. Non-participation of Deoxyribose-I-Phosphate in Trans-N-glycosidic Reactiong Trans-N-Glycosidic Reactions in the Deoxyribose N~cleoside Series Enzymatic Formation of New Deoxyribosides 3S8 V. Phosphorylation of Nucleosides 390 VI. Incorporation of Purines and pyrimidines into Nucleic Acids. 39I Inviv() Studies with Labelled Purines 39I. -In vivo Studies withlabelled pyrimidines In vitro Studies with Labelled Purines Studies on the Amphibian and Echinoderm Egg Studies on Micro-organisms 394. Reference" C1""'.."'.., 395 J Nucleosides and Nucleotides as Growth Substances for Microorganisms. By W. S.. McNuTT, Vanderbilt University, School of Medicine, Department of Biochemistry, Nashville, Tennessee. 401 Introduction. 402 I. Nucleosides and Nucleotides of Ribose 405 I. Coenzyme I, '.Desamino.codehydrogenase I," Coenzyme II and Nicotin;. amide Riboside : 40.S

8 - x Inhaltsverzeichnis. --Contents. -Table des niatieres. 2. Purine-Nucleosides and Nucleotides. ~o.s a) Growth-promoting Activity : 4.S b) Growth-inhibiting Activity and the Ability to Reverse Growthinhibition Nucleotides in the Nutrition of Lactobacillus gayonii pyrimidine-nucleosides and Nucleotides 411 a) Growth-promoting Activity 411 b) Growth-inhibiting Activity 412.s. The Biosynthesis of Ribosides and Ribonucleotides ~I3 A Comparison between Microorganisms and Higher Animals with Regard to Purine Precursors in Nucleic Acid Biosynthesis Vitamin B Microbiological Functions of Vitamin B Different Forms of Vitamin B12,.419 II. Nucleosides and Nucleotides of Desoxyribose 420 I. The Biosynthesis of Desoxyribosides : Considerations of the Mode of Formation of the Desoxyribosidic Linkage....: The Growth-promoting Activity of Desoxyribosides and Desoxyribonucleotides. 424 a} The Specificity of Certain Desoxyribosides in Eliciting the Growthresponse of Bacteria.,.424 b) The Non-specificity ofthe Natural Desoxyribosides in Promoting the Growthof Certain Bacteria, The Relationship of the Desoxyribosides, Vitamin B12, Reducing Agents, and the "Citroverum-Factor" in Supporting the Growth of Various Microorganisms. 426 Relationship between Certain Reducing Agents and Vitamin B12 Requirement 427 The "Citrovorum Factor" ~31 References. 33 J Some Current Concepts of tbe Chemical Nature of Antigens and.antibodies. By DAN H. CAMPBELL and N. BULMAN, California Institute of Technology, Pasadena, California. 443 I. Introduction. ~43 II. Antigens and Haptens ~45 I. Antigens Haptens ~~9 III. Antibodies ~5 I I. Chemical Composition of Antibodies ~5I 2.. Electrophoretic Properties of Antibodies. ~5z 3. Shape and size of Antibodies Nature of Combining Sites : ~55 5. Purification of Antibodies ~6I

9 XI d~si Inatie:re$. t~,~..?j,;ti~, -,Physical Nature o.f'.antigen-antibodyreactions 463 :i. The Properties of Specific Precipitates. 463 a) Composition. 463 b) Formation and Specificity 465 c) 'Ageing' Thermodynamic Properties of Antigen-Antibody Reactions. 466 a) The Free Energy and Heat Changes in Antigen-Antibody Reactions 467 b) Differences in Free Energies of Combination. ; Nature of the Force$ Involved MatheInatical Interpretations of the Precipitin Reaction. 475 '5. A Note on the Use of Polyvalent Haptens 476 V. Conclusions. ; 477 References. 478 Namenverzeichnis. Index of Names. Index des Auteurs. 485 Sachverzeichnis. Index of Subjects. Index des Matieres