Ref. 547.7082 ZEC V.1 CONTENTS
Neuere Richtungen der Glykosidsynthese. 1 I. Alkylglykosid-synthesen aus freiem Zucker und Alkohol mit chemischen Mitteln 1 II. Biochemische Synthesen 1 III. Synthesen aus Acetohalogenverbindungen 2 IV. Umwandlung von β-Glykosiden in ihre α-Form 2 V. Quecksilbersalz-methode 6 VI. Darstellung der Bioside der α-Reihe ohne Anwendung der Acetohalogen verbindungen 15 VII. Phenol-glykosid bzw. Phenol-biosid-synthesen nach HELFERICH, mit Hilfe von Zink Hloid bzw. P-Toluol-sulfonsaure 18 Literaturverzeichnis 20 The Component Glycerides of Vegetable Fats. 24 I. Attempts to Isolate Individual Triglycerides from Fats by Crystallisation 25 II. Crystallisation of Hydrogenated or Brominated Fats 26 III. Quanthitative Studies of the Componet Glycerides in Natural Fats 27 References 50 Recent Advances in the Chemistry of the Sterols. 53 Stereochemistry of the Steroids 53 i-Cholesterol 60 Oxidation of Cholesterol 62 Bromination of Steroid Ketones 71 Ergosterol and its Photoisomerides 81 Phytosterols and Sterols of Lower Animals 91 References 94 Cozymase. 99 I. Biologische Institung der Cozymase 99 II. Darstellung und Eigenschaften der Cozymase 102 III. Konstitutionsermittlung 106 IV. Ist Cozymase ein phosphat-ubertragendes Coenzym? 115 V. Derivate der Cozymase 116 Nucleinsauren 121 I. Einleitung 121 II. Allgemeine Bedeutung 121 III. Konstitution der Nucleinsauren 125 Literaturverzeichnis 156 Chlorophyll. 159 I. Die fruheren Arbeiten (1904-1913) 160 II. Die neueren Arbeiten (1927-1932) 168 III. Ergebnisse der Jahre 1932 bis Mitte 1938 184 IV. Bacterio-chlorophyll 222 V. Protochlorophyll 227 VI. Funktion und Zustand des Chlorophylls im Blatte 229 Verzeichnis der Chlorophyllsubstanzen 233 Literaturverzeichnis 238 Anwendung physikalischer Methoden zur Erforschung von Naturstoffen: Form und Grobe dis- Pergierter Molekule. Rontgenographie. 255 I. Bestimmung von Form und Grobe der Einzelmolekule im dispergierten Zustand 257 II. Die rontgenographische Untersuchung in festem Zustand 298 Literaturverzeichnis 346 Namenverzeichnis 352 Sachverzeichnis 362
Ref. 547.7082 ZEC V.2 CONTENTS
Lignin. Von Professor I I. Einleitung I 2. Verwandte Pflanzenstoffe 2 3. Zuslierung 3 4. Isolierung 4 5. Physikalische Eigenschaften 5 6. Analytische Unterlagen 6 7. Lignin als Derivat des Phenylpropans 7 8. Uber die Konstitution des Fichtenlignins 7 9. Funktionelle Derivate 10 10. Substitutionsprodukte 10 11. Unmittelbarer abbau 11 12. Abbau nach Aufschluβ mit Alkali 12 13. Abbau nach Aufschluβ mit Bisulfit. Ligninsulfonsaure 14 14. Abbau nach Aufschluβ mit Thioglykosaure 16 15. Abbau nach Aufschluβ mit Alkoholen und Mineralsauren 16 16. Abbau nach Aufschluβ mit Hydrazin, sowie mit Kalium in Ammoniak 18 17. Dehydro-diisoeugenol und seine Umwandlungsprodukte als Modelle 18 18. Andere Modelle 19 19. Coniferylalkohol als Modell 20 20. Schluβbetrachtung 21 Nachtrag 23 Literaturverzeichnis 24 Flechtenstoffe. 27 A. Verbindungen der fettreihe 28 B. Verbindungen der Benzolreihe 33 Flavine. 61 A. Allgemeines 61 B. Die synthetischen Verfahren 75 C. Flavine als wasserstoff-ubertragende Cofermente 90 Literaturverzeichnis 98 Chemistry of the iodine compounds of the thyroid. 103-129 The structure and synthesis of vitamin C (ascorbic acid) and its analogues. 132-156 Neuere Richtungen der Oligosaccharid-Synthese. 160-207 Chitin und seine Spaltprodukte. 212-240 Tabak-alkaloide. 248-292 La spectrochimie de fluorescence dans I’etude des produits biologiques. 301-336 Namenverzeichnis 342 Sachverzeichnis 352
Inhaltsverzeichnis. Seite Bedeutung der Dien-Synthese filr Bi1dung .Aufbau und Erforschung von Naturstoffen. Von Prof. Dr. 0. DIELS, Universitjtt Kiel I Einleitung. Eigenart der Dien-Synthese I I. Bedient sich die Natur der Dien-Synthese als Aufbaupcinzip ? 3 II. Kiinstliche Gewinnung von Naturprodukten durch DieD-Synthese 6 I. Dien-Synthesen in der Reihe der Terpene und Campher 7 2. Dien-Synthesen in der Reihe des Cantharidins II 3. Dien-Synthesen in der pyrrol-Reihe , 4 4. Dien-Synthese in der Lupinan-Reihe 17 III. Die Dien-Synthese als Hilfsmittel zur Erforschung von Naturprodukten 21 Ausblick. 26 Literaturverzeichnis. 27
Biochemische Hydrierungen. Von Professor Dr. F. G. FISCHER. Univer. sitat Wiirzburg 30 I. Einleitung 30 II. Die Hydrierung der Athylenbindung ...; 31 A. Hydrierungen durch Hefe und Bakterien 32 I. Primare Alkohole 32 2. Aldehyde. 34 3. Ketone. 35 4. Sekundare Alkohole 38 5. Ketosauren. 39 6. Stoffe mit konjugierten Doppelbilldungen 4° 7. Allgemeine Bemerkungen 42 B. Hydrierungen im Tierkorper 45 I. Alkohole und Aldehyde 47 2. Ketone. 48 3. Allgemeine Bemerkungen 50 C. Stereochemisches %U den Athylenhydrierungen 51 III. Hydrierungen in be80nderen Stoffgruppen 53 A. Steroide ~; 53 I. Sterine 53. a);Die Hydrierung von Cholesterin zu Koprosterin 53. b) Zur Frage der Bildung von Gallensauren aus Cholesterin 55. 2. Ga1lensauren : 56 3. Steroide Hormone 59. a) Reduktionen mit Hefe 59. b) Hydrie- rungen und Dehydrierungen mit Bakterien 62. 4. A1Igemeine Bemerkungen 65 IV Inhaltsverzeichnis
Seite
IV. B. Die Fettsauren.., Fermentsysteme biochemischer, , Hydrierungen , . : b7
71 3.2.I. Die Die CarbonylhydrierungAthylenhydrierung Hydrierung der Carbiminbindung. , .., ., ..., 71 72 74 Literaturverzeichnis ,..,...:, ,. 75
Gallenfarbstoffe. Von J)ozentl)r. W.SIEDEL. TechnisCheHochschuleM(inchen 81 l..::inleitung , 81 II. Vorkommen der Gallenfarbstoffe. Bildung und Ausscheidung. R2 I. Bildung des Bilirubins.. X2 2. Umwandlung des Hilirubins im Organismus S4 3. Zur Bilanz des Hlutfarbstoffwechsels X6 III. Vierkernige Gallenfarbstoff" (Bilirubinoide) 87 1. Bilirubin, Mesohilirubin. Dihydrobilirubin 1j7 Bilirubinsaur", Xanthobilirubinsaure XX ..Ni:ritkorper.' 91 Neoxanthobilirubinsaure. Mesobilirubin-XiIl.1X 91 Synthesen der Xantho-. Neoxantho-! 1so-neoxanthobilirubinsaure ; Mesobilirubin-III:IX 9:! Nomenklatur der Bilirubinoide 96 Synth,ese des Mesobilirubins-IX,IX 97 Konstitution des Bilirubins. Dihydrobilirubin 9X Farbreaktionen des Bilirubins und Mesobilirubins '1'1 Ober den physiko-chemischen Zustand d.es Bilirubins im Blut und Harn 101. a) Bilirubin-Albumin 101. b) .,Aktives.' Bilirubin 101;. 2 Ferrobilin, Glaukobilin. Biliverdin; Mechanismus der (~allenfarbstoff. bildung ro1; Ferrobilin. (;lat1kobilin rO1; Biliverdin \Uteroverdin) 104 Ober die Aufspaltung d~ Porphyrinringes zu Bilirubinoiden sowie tiber die Konstitution derVerdoha.mochromogene und den Mechanismus der Bilirubinbildung a) Chemische Aufspaltung des Porphyrin- ringes 105. b) Physiologische Aufspaltung des Porphyrinringes 10S. c) Photochemische Aufspaltung des Porpflyrinringes 1O'J. 3. Bilipurpurine. Choleteline; Mechanismus derGMELINschen Reaktion. .~O'J 4. Urobilinogen und Stereobilinogen 112 Urobilinogen (Mesobilirubinogen-IX.tX) 112 Stercobilinogen 113 Nachweisreaktion fiir die Bili-chromogene 113 Reaktionen zur \Jnterscheidung von Urobilinogen und Stercobilinogen 113 5. Urobilin, Stercobilin 114 Na~hweisreaktion des Stercobilins und Urobilins 1 IS Unterscheidungsreaktion zwischen Urobilin und Stercobilin. 11S (). Dihydro-mesobilirubin IlS 7. Mesobiliviolin. Mesobilirh()(lin ; 11,> Phykobiline, die Pigmente der Rotalgen; Mesobilierythrin. Mesobili- cyanin 121; Typen der bis jetzt.bekannten Hilirubinoide (Tabelle 1) 12.1 I-ichtabsorption un,1 Kon!!titution dt'r Bilirubinoide 124 - Inhaltsverzeichnis v
Seite IV. Zweikernige Gallenfarbstoffe , 125 I. Mesobilifuscin, Bilifuscin, Myobilin 125 Mesobilifuscin 125 Bilifuscin. 128 Myobilin 129 2.. Pentdyopent 13° V. Gallenfarbstoffe unbekannter Konstitution 131 1. Porphobilinogen. 131 2.. Rubrobilin 132 3. Biliprasin 132 4. Bilihumin I3i 5.. Choleprasin 13J. 6.. Bilinigrin, Dehydroxy-bilirubin 13J. 7.. Kopronigrin 132 8. UrochromB , :.. 132 9.. Xanthorubin 133 Literaturverzeichnis. I~~
The chemistry of the lipoids of the tubercle bacillus and certain other microorganisms. l3y ProfessorR. J. ANDERSON, Yale Uni- versity. New Haven (Conn.). USA. 145 Introduction J45 Methods. 147 Separation of the alcohol-ether soluble lipoids J48 Propertie& and composition of acid-fast bacterial phosphatide& J5O Cleavage products of the phosphatides on. acid hydrolysis J52 The acetone-soluble fats of the acid-fast bacteria J56 Saponification of the fats and sep"Tation of the cleavage products. 159 The fatty acids. The solid saturated acids. J59 The liqui
Seite Are sterols metabolic products of acid-fast bacteria 187 The The lipoids phosphatideof PhytomonasLactobacillus of.Lactobacil1us tumefaciens.acidQPll.ilus acidophilus. .. .89
191 193 ThcR"ferenr"" Thcyeast lipoids of phosphatides yeast.. 194 195 107
J Recent work on the configuration and electronic structure of
molecules; with some applications to natural products. By
Professor LINUS PA ULING, California Institute of Technology, Pasadena
TheInteratomicIntroduction. !California),USA.electronic distances theory , , of .,and , valence ..'! bond forangles non-resonating in , , non-resonating ! molecules. ' organic molecules. . 203 203 2°5 207
TheCoplanarityTheIsomerismTheReferencesResonancel{estrictedrotation structureeffectstructuredistances andofand of resonanceof ofof conjugatedstructuremolecular theresonating non-bonded abbut a.nthocyanidins on of configurationsinglesystems interatomicthemolecules contact car.otenoidsboi1ds of distances. atoms:. ?r)
215 218 220 222 227 22q
Namenverzeichnis 2,6
Sachverzeichnis 2A"- ~
Inhaltsverzeichnis. Seite l' Die Chemie der pflanzlichen Herzgifte, Krotengifte, Saponine und Alkaloide der Steroidgruppe. Von RUDOLF TSCHESCHE, Berlin I I. EinIeitung I II. Die Herzgiftaglykone derCI3-Reihe 7. III. Di6 Herzgiftaglykone der C1.-Reihe 6 IV. Die Glykoside S V. Pie Kr~tengifte 17. VI. Die Sapogenine der Steroidgruppe 1(, VIl. Die Alkaloide der Steroidgruppe :J; 1 .. Zur .lteraturverzelc Bio:chemie derh nlS. .;" Vitamin B-Gruppe (Pantothensaure. und
Vitamin B6. Von THEODOR WIELAND und IRMEXTRAUT Low, "' Heidelberg J;~ Die Pantothensa.ure. J;8 I. Entdeckung 28 II. Bio1ogische Wirkungen , 29 Ill. Konstitution 30 IV. Synthesen. , 32 I. Synthesen von fJ-Alanin und seineIi Estern , 33 7.. Synthesen de's !X-Oxy-fJ.fJ-dimethyI-y-butyro1aktons.. 33 Spaltung des racemischen (X-Oxy-fJ.fJ-dimethyl-y-butyro1aktons in die optischen Antipoden , 34 3. Verknilpfung der Spaltstilcke : 35 Anspaltung der racemischen Pantothensa.ure 37 ...Bio10gische Synthese ; ..37 . 1 V. Konstitutionsspezifita.t ; 38 I. Verbindungen mit unvera.nderter Laktonko!Uponente 38 7.. Verbindungen mit unvera.nderter fJ.Alaninkomponente 39 3. Verbindungen mit vera.nderter fJ-Alanin- und DioxySa.\N"ekomponente 42 VI. Nachweis und Bestimmung 42 f Literaturverzeichnis. 43. })as Vitamin B. ; 46 I. Einleitung ; '.. 46 II. Physio1ogie. ; 46 III. Vertra.glichkeit und Abbau im Tierkorper 48 Iv. Mikroorganismen und Pflanzen ~ , 48 V. Vorkommen ; ..., ; 50 VI. Iso1ierung , , 50 \I.II. Konstitution und Synthese 51 VIII. Eigenschaften ; 54 IX. Nachweis und Bestimmungsmethoden 57 I. Bio1ogische Verfahren 57 7.. Chemische Verfahren , :.; 58 Literaturverzeichnis. ~. 60 IV I nhaltsverz.'ich nis
Scitc
Pterine, Vori I{OBERT Pl'HH~IA:-;:-;, ~Iiinchcn"""""""""""", 64
[. Ptcrinsynthcsen """""""""""""""""""""",.,"" 65 II, Eigenschaftcn urul [{eaktionen dcr l)eri\'ate desPteri\lin:;"""""", io [I I I~as Vorkomm"n cter Pterine in tler ;.;atl1r urul ihre ( ;e".innl1ng , , , , , , , i6
I Schmetterlingl' """"""""""""""""""",.,:,""" i6
J. Andere Insekten, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , . i9
3 \~'irbe[tiere"".." """,.,...,."..,.".""..."..;,...,. 80
.[V. OieI. Insekten",.,."" bio[ogische Bedeutung (ler ,."".".., l"terine , ,',..,. 8'2
82
J. Saugetiere , , , , , , ..' , .., .., ..., ., ., , , ., , ., , , , .. 84
I.i te rat l1 rverzeich i:; ., , , , , , , , , , ..., , ., .., , .., ., , ..' .., .. 8-,
Die Biochemie der Virusarten. Von GERHARD SCHRAMM , Hl'rlin-1 )al\ll'm ~7
[ , Ein[eitung , ..., ,. , ., ., ., ., , , , , ,
[I. DefinitionBio[ogie der des Viren,.,.., Virusbegriffe:;.,.., ".",..,."..,." ,...,."""., " ,. 8Q
[. ()bersicht tiber tlie Viruskrankheiten,..,.,..,.", "" " 89
4.6,3.5. J.. DieVerhaItenDieTumorbi[dungDieJ)ie VbertragungEntstehungderVirusvermehrung des' Virus , .,durch Viren,."..,im., .., \Virt Viren...,...,, ..., , , ., , ..., , ..., , ., ,."...,..,;,."..,.....,, """,..,.".., , , , , ,..., .,, , ., , , .., , , 92 93 93 96 ')9
[II. 7.Methoden Die Veranderlichkeit der Virusforschung.,..".,...,..,..,."., der Viren,."" " ,...""", "". 10[
[ , Biologische Meth(jtlen , , ., , , ..., .., .., , , , , 10.5
J.. Die Reindarstellung der Virusarten, , , ,... 109
b)a) ChemischeDie Ultrazentrifuge Verfahren , '.' , , ., .., , , ., , , , , ., , ..., , , .., ., ., , .., , ., , , ..., , .., . 109
III
4.3. b)a)d)DieDie c) BestimmungDieBestimmungDie physika[isch-chemische Prtifung elektronenmikroskopischeE[ektrophorese.",;., auf desdesder Einheit[ichkeit TeilchendurchmessersMoIeku[argewichtesGestalt Kennzeichnungder ~-irenUntersuchung , "',."."..".,.,.,..,:.,.mit , durch der der Virusarten {ltrazentrifugeLltrafiltration." ,.., , , I I. ;)
116 , ,x
121
122
125
e) Die e[ektrochemische Charakterisierung der Viien , ..., ., ., ..., .. 131
5.. a)Die Das sero[ogische Antigen. Charakterisierung.., , der .., .., Viren , ., , , ., , .,. .., , ,. , .., , .,' 136
137
b) Der Antikorper ...,. , , , " .., , ., , ., , 13!3;
c) Die Antigen-Antikorperreaktion , ,.""... 138
d) Feststellung der Verwandtschaft..., ,.., ".,. 141
e) Reinheitsprtifung und Na.chweis der ~-iren..,.,.., ,;. 41
IV. Chemische f) Rtickschliisse Eigenschaften auf die der chemische ~..iren Zusammensetzung der Vireri ,"" 143
144
I. b)a)Zusammensetzung c) VerhaltenVerhalten gegengegengegen und chemlschephysika[ischeEnzyme chemisches Einwirkungen Einfltisse ~..erha[ten " , , ..,, .., , .,, .., ., ,',...,.., .,. 144
144
145
148 I nhaitsverzeichni;; v
S,.jt,.
I ~.f ~. a)Oie Vorkornmenf)as einzelnen T;\bakmoSaikvirl\s Viru8arten14'!. -Darstellung (jWa..mol. 150. t{/.baci Das var. Vcrhal.ten vutga..e) in I.bsl\n~ , :'.. 15!
I~.j
-GroUe und (;estalt 153. Elektrochemischc Eigensehalten 153
Zusarnrnensetzung 154. Str1lktur des Tabakrnosaikvirus 155.
b) Bi010gischeOie Varianten Eigenschafte1\ de8 Tabakmosaikvirus 161. Serologischt'8 Verhalten, 10.~.
GroUe und (~estalt 16(); -Chemisches Verhalten 106
I('~ c) Bi010gieDie Kartoffelviren der Kartoffelkrankhe1ten 108. f)a!; Kart()ffel-X-Virlls 1!"1
-Das Kartoffel-Y-Yirus 170
(
d) Das Tabakringfleckenvirus 17Q
e) Das Severe-Etch-Virus ~ 17r
f) Das Tomaten-Bushy-stunt-Virus '7'
g) Das Tabaknekrosevirus 'i3
h) Die Polyederviren der lnsekten li3
j) Das .Virus deF Maul- und Klauenseuche ; li5
k) Das Encephalornyelitisvirus der Maus r7!'
I) Das Virus der Kinde!"lahmung (Polyornyelitis) 177
m) Das Kaninchenpapillornvirus ;, 17~
n) Die E~ementarkorper der Vaccine , 180
0) Die Ba'kteriophagen 18;:
Literaturverzeichnis. ; ,!\~
Biologische Oxydationen. Von KARL BERNHARD 1Ind HAROLD
TI. I. 4.3.~.EinleitungDie 1. LINCKE. b)d)b)Bildunga)brc)Bildunga) c) Bildung einzelnen 1.EntstehungOH-GruppenKetosa.urenDurchKetosa.~renOH-Gruppen Aromatische vonvonvonZiirich oxydativeDesaminierung oxydativen CarbonylgruppenCarboxyl-GruppenAldehydgruppenHydroxylgruppenausausvon anbeibei RingeAminosa.urenOxysa.uren Ketonenhydrocyclischenheterocyclischenaromatischenaliphatischen Aufspaltung Prozesse 210. -~. von VerbindungenVerbindungen RingenRingen HydrocyclischeRingen. ; ; ; Ringe ~11.' - 1X~
18H
190
1(!0
1',10
Iq1
1"-,,:1
1<)7
ly7
19'1
.I<)<)
!00
20!
204
!0,!
210
3. Heterocyclische Ringe 212.
c) Aus1. Oxydation MethylgI;uppen am ~nzolkern befindlicher CH3-Gruppen ~15. - 214
,,~
2. Methyloxydationen natiirlicher Fettsa.uren215. --3. Methyloxy-
dationen substituierter Fettsauren 2 r 7.
~-sta.ndige Gruppen 217; p-sta.ndlge Gruppen ~18 ; y: undE-standige
GruRPen !19 VI Inhalt"vf'rz"i,.hni"
," ", 4 Methyloxydationen bei Polyencarbon!;auren 220. 5. Methyloxy- c) Durch Schimmelpilze ;..., " 286 d) Hemmende Wirkung zwelwertiger Kationen auf den Abbau der Citronensa.ure , , ., ; 287 e) Bemerkungen zur energetischen Koppelung , 287 3. Abbau der p-Ketocarbonsa.uren iiber denCitronensaure-Cyclus. (Bildung der Citronensaure aus p-Ketocarbonsauren und Oxalessigsaure) 290 ,,\ Ahh,,11 (l"r A(""t""";""ji,,rp ;n N;pr" llnn Hpr7m11"l-pl ?00 Inhaltsverzeichnis. VII Seite c b) .-\bbau der {1-I\etocarbonsa.uren ({1-0xydativer Abb~u ~!er l;e.ttsa.u~~n) 290 C) Bemerkungen zur Koppelung des Kohlenhydrat- un(l-Fettsa.ure- abbaus. ; 291 4. Intermedia.rprodukte der CitronenSa.Uresynthese 292 a.) Beim Abbau der Brenztraubensa.ure ...; : ~92 b) Versuche mitsignierter Oxalessigsa.ure und Trideuterioessigsa.ure zur Kla.rung des KondensationSmechanismus 295 c) Zusammenfassende Betrachtungen tiber den ReaktionSVerlauf bei der CitronenSa.urebildung 298 5. Bemerkungen zu den Einwa.nden gegen die Theorie des CitronenSa.Ure- cyclus 303 6. AIlgemeine Bemerkungen zur bakteriellen Ga.rung 306 7. Die PropionSa.Urega.rung ; 308 a) Bildung der C4-DicarbonSa.Uren ...; 309 b) Zur Bildung der C3-Korper (PropionSa.Ure. BTS und Milchs1j.ure) .310 C) BildungderEssigs~ure 315 8. Die Buttersa.ure- und Butanolga.rung 317 9. Abbau der Essigs~ure. CitronenSa.Ure und Acetessigsa.ure 318 a) Abbau der Essigsa.ure 318 b) Abbau derCitronenS~Ure 324 c) Abbau der Acetessigsa.ure durch B. coli. 329 10. SchluGbemerkung 331 Literaturverzeichnis 334 Ober monomolekulare Filme an Wassergrenzflachen und iiber Schichtfilme. Von H.J. TRURNIT, Heidelberg 347 Namen und Zeichen 347 Einleitung 348 I. H-Filme. 352. I. Einfache Erfahrungen an Wasseroberfllichen 352 2. Methoden der Schubmessung 354 3. Anderung des.Yo1tapotentials 356 4. Das thermodynamische und mo1ekulare Bild der Filme 358 a) Expansive Filme : 360 b) Kondensierte Filme 364 c) GedehnteFilme , 369 5. EinfluB des Substrates 37I 6. Filme von Kettenmo1ekiilen mii Doppelbindung 372 7. Filme von Sterinenund lihnlichen Verbindungen 373 8. Filme von Kohlenhydraten und synthetischen Po1ymeren. 376 9. Filme von anderen Stoffen 377 IO. Indicatorole 377 II. Spreitungsmechanismus. Bewegung in Grenzfllichen 378 I2. UltramikroSkopische Beobachtung 382 I3. .Viskositlit 382 I4. Elektrische Leitfahigkeif.., 384 I5. Verdampfung durch Filme hindurch 384 I6. Mischfilme und Wechselwirkung 385 I7. Reaktionen derFilme 390 ~ Seitc 18. l3eitI:age zu Probleml'n tler Physiologie und Pharmakol()gie 394 II. 20.21.K-Filme.22.26.25.23.24.19. ErgebnisseI'ilmeHl;rstellungMechanischeUntersuchungenElektrischeP-Filme anan (~keletonder andererEigenschaften und Eigenschaften (;renzeGrenze mitMcssung films) ljntersuchungenRontgen- fl/flf/fi .., und Elektronenstrahlen ... 398 39() 4.00 401 404 407 409 410 410 b)a) ElektronenstrahlenRontgenstrahlen /.. 412 m.. 3°.27~28.29.3I.EiweiBfilme.32.33.34.35.36. VerdampfungWirkungRestfilmeK-FilmeS-SchichtenAllgemeineb)d)Unt~rsuchungstechnikDasSpreitungsmethodena) Spezielle e)c) f) F/A-Abhangigkeit,DenaturierungDickeHomogenitatSpreitungsdauer. Spreiten undals.der vonEigenschaften Eigen~chaftenSchutzschichten L1V/A-VerhaltenFilme,vonUV-Licht derder K-Filmen Mo1gewichtsbestimmungenFilmeSpreitungsflache auf K-Filme vom PH :... 413 413 414 415 415 415 416 417 418 420 423 423 427 432 432 435 439 IV. T"iteraturverzeichnis.37.40.38.39.42.41.43.Ausblick., h)g) Mischfilme FilmeSpezielleK-FilmeReaktionenFilmeanderStrukturi) ElastizitatViskositatKompressibilitat an Untersuchungenderder .j an FilmeGrenzeGrenzefi/fi' , Filmen fest/fiiissig. : (S-Schichten) ~ 440 442 442 444 445 446 447 457 458 463 467 Namenverzeichnis 477 Sachverzeichnis 492 Inhaltsverzeichnis. Contents. -Table des l}1atieres. Carotinoid-epoxyde und furanoide Oxyde von Carotinoidfarb- stoffen. VonP. KARRER, Universit!!.t Ziirich I I. Vorkommen, Konstitution und Pattialsynthesen der Carotinoid-epoxyde I II. Die futanoid gebauten Carotinoid-epoxyde 6 III. Die Molekularsttuktur der Carotinoid-epoxyde 12 IV. Biologische Bedeutung det Carotinoid-epoxyde 14 I Literaturverzeichnis 17 I Some Biochemical Aspects of Marine Carotenoids. By D. L. FoxJ Scripps Institution of Oceanography of the University ofCalifornia, La Jo!la, California. ' 20 Introduction 21 Marinemuds 21 Marine animals in general. 23 Protista. ; 24 Sponges 25 Coelenterates 26 Worms 27 Echinoderms. 28 Mollu$ks , 29 , Cru$taceans 30 Tunicates 3 I Fishe$ 32 Mammals 34 Conclusions. 34 Ref er en c e$ 36 Azulenes. By A. J. HAAGEN-SMIT, California I,nstitute of Technology. Pasadena, California. 40 Introduction. 40 I$olationandpurification 41 Physicalproperties 41 Chemical properties. : 44 Structure determination 45 Nomenclature. 46 Structure of naturally occuring precursors of azulenes 47 Syn!hesis of Azulenes 49 Absorption spectra. 57 ~ Some bioche~ical aspects. 62 , Further possible types of azulenes 65 " f Pharmacological properties ofazulenes 66 ..J References 67 Recent Advances in the Study of Component Acids and Com- ponent Glycerides of Natural Fats. By T. P. HILDITCH, The , Introduction: UnivetsityofLiverpool Discussion of the ..Rulp; of even, distribution" 72 72 _:;' IV Inhalts""~zei,,hni~ -Contents. Table des matiere... Spectrophotometric determination of certain unsaturated higher fatty acids. .75 Resolution of mixed fatty acids by crystallisation from solvents at low tem- peratuces A6 Partial resolution of mixed glycerides in natural fats by crystallisation from solvents at low temperatures : ; 81 The present state of knowledge of the glyceride structure of natural fats. .86 I. Fats with three (or at most four) major component acids. 86 (a) Fats in which saturated acids predominate over unsaturati,d (oleic) acids 86 (by Fats in which oleic. linoleic and/or linolenic acids predominate. 87 2. Computation of component glycerides from the proportions of the com- ponent fatty acids in a fat 88 3. Fats with four or more component acids in similar proportions 89 4. Animal body fats rich in stearic acid and animal milk fats containing notable proportions of butyric and/or other lower saturated acids. 90 (a) Animal body fats. 90 (b) Animal milk fats. 93 5. Synthesis and transformation by chemical means of mixed glycerides in the laboratory. 95 References. 96 Enzymatically Synthesized Polysaccharides and Disaccharides. By W. Z. HASSID and M. DOUDOROFF, The University of California, Berkeley, California 101 Introduction. 101 Formation of starch and glycogen through the phosphorolytic condensation. .102 Conditions affecting polysaccharide formation. 104 Synthetic polysaccharides 106 Arsenolysis and phosphorolysis of amylose and amylopectine.. 107 Phosphorylase. 108 The mechanism of dextran and levan formation. 109 M~hanism of sucrose formation ; " 111 Specificity of sucrose phosphorylase 115 D-glucosido-D-xyloketoside, D-glucosido-L-araboketoside and D-glucosido- L-sorboside 116 /X-D-glucosido-L-arabinose LIS Formation of sucrose and other disaccharides through exchange of glycosidic linkages. 121 References. 123 Recent Developments in the Structural Problem of Cellulose. By E. p ACS U, Princeton University. and The Textile Foundation. Princeton. . New Jersey 128 I. The linear structure of cellulose 128 Introduction 128 Critical review of the proofs supporting the linear structure of cellulose 13° I. Nature and uniformity of the building units 130 2. Location and number of the free hydroxyl groups 13° 3. The chemical proof of the constitution of cellulose. 131 4. The polarimetric proof of the constitution of cellulose. 132 5. The kinetic proof of the constitution of cellulose. T Inhaltsverzeichnis. -Contents. -Table des matieres. v 6. The static proof of the constitution of cellulose. 134 1. The X-raypatternofcellulose.' 134 I Molecular weight determination of cellulose. 135 A. Chemical..methods , .., 135 B. Physical methods. 138 Oxycellulose 140 Hydrocellulose ; 144 Conclusions regarding the linear structure of cellulose. 145 II. The laminated chain structure of cellulose 146 Theoryof eeter linkages 146 Theory of blocked hydroxyl groups 150 Theory of looping bonds 151 ~ I. Theory of acid-sensitive bonds and the principle of periodi6ty 155 Theory ofacetallinkages in equi-distant open-chain units and the laminated chain structure of cellulose..; , : 158 A. Heterogeneous and homogeneous degradation of cellulose in acidiC' media. '0 158 B. The co.ncept of,:limit hydrocellulose" 160 C. Proposed structure of cellulose 163 j Li::::~e:;e; ..~.. ~~~.~~~~ .;~~ .~~~~~~~~ '~f..;~~~r. ~~~~~~: .~~~:e~~~: 17° , \ Wisconsin. , 175 I. Occurrence, formationand detection : 175 .: The state of lignin in wood 175 Lignin-complexes in wood 179 Formation, detection and estimation of lignin. 180 II. Isolation 9f ligniri 182 III. Properties and convers.ions of lignin 186 ~ Physical properties 186 Various conversions. 188 Vanillin from lignin. 192 Oxidation, reduction and halogenation. 193 Nitration 195 Sulfonatiori 195 Ethanolysis of wood and lignin 199 Hydrogenation. , 200 E~periments on the synthesis 0£ lignin and similar products. 208 Decomposition 211 1 IV. The strqcture of lignin 213 ERDTMAN'S concept of the lignin structure. 213 FREUDENBERG'S concept 0£ the lignin structure. 217 HIBBERT'S concept of the lignin structure. 217 Conclusions. 224 ' I T:ee£~~::i:~~. .~.; .~~~ .~~~~~~~~.~~~ ..~~. .;~~~ .~~~~~~~ ..~; 225 I!; V. DEULOFEU, Facultad de Ciencias Exactas, Fisicas y Naturales, t BuenosAires, Argentina 241 \ Introduction.. 241 t - VI I~t$v~rzeichBiS.;'-CQt1te~. ~ Tabl6des matier~~ ~ I. The b\\fagins ; " 242 i} Main representa,tives of tht1 b\\f9talin class. 246 ¥,~ B\\fotalin 246 Marinob\\fagin ,. : 249 :f Gamab\\fagin (gamab\\fotalin, gamab\\fogenin) : 249 f~. 1 Cinob\\fagin., 25° ;;. Cinob\\fotalin, B\\falin. 252 PSe\\do;.desacetyl-b\\fQ:tali~ 252 .Pharmacology of the b\\fagins 253 , II. B\\fotoxins. 254 \ Main representatives of the b\\fotoxin class. 255 B\\fotoxin 255 Arenob\\fotoXin , 256 Gamab\\fotoxin 256 Marjnob\\fotoxin. 256 Pharmacology ofthe bufptoxins 256 III. Basic constituents oftoad venom.s 257 Buiotenine 257 Pharmacology of bufotenine 259 Bufotenidine 259 Pharmacology of bufotenidine 260 Bufothionine , ; 26() D~hydro-bufotenine 261 Pharmacology of dehydro-bufotenine , 261 L-Adrenaline :.~ , 261 JV. Ster9ls ..., : 262 .V. Suberic acid 262 References. 262 j Biochemistry of Fish Proteins. By E. GEIGER, The University of Southern Californi~! LoS Angeles, C~lifornia , ' ..267 Introduction. , , 267 Composition of fish m\\s(:leprotein , 268 Amino a(:id content 0( fish muscle protein,..., , 272 Nutritiveval1)e Qf fish protein ,.., , 275 ,Feeding experiments 275 .Evaluation of results 281 .Fish blood proteins. 284 Fish collagens. 287 Fish proteins wit~ enzyrnaticactivity , 289 Proteins i~olat~ frornfish s~rm 289 Pharmacologic~l effects of some histones and protamins. 291 PI'oteins iSolated (rom female reproductive organs of fish. 294 References ,." ,.,. 294 Some Recent Developments in Chemical Genetics. By G. ,W. BEADLE, California Institute of Technology. Pasadena,. California. ; , 300 Classical genetics. ; 300 Chemical genetics., , , 302 ~ -- . IDhaltsverzeichnis. -Contents.- T{\ble des mB.tieres. .vu Phenylalanine metabolism. 304 ~ ,.' Antigen specificity. 306 iii , " Hemophilia. : 307 Gene.directed specific reactions in other organisms. 308 Neurospora 310 Nature and action of genes 317 Gene mutation 3.18 Universality of genes ,320 Cytoplasmic factors. 321 Genes and evolution. : ..324 Conclusions ,.3~6 References. 326 Infrared Spectroscopy in Structure Determination and its Application to Penicillin. By R. S. RASMUSSEN, Shell Develop- ment Company, Emeryville, California 331 Introduction 331 I. Experimental methods. 332 I. Instruments. 332 2. The transmission curve , 333 3. Absorption cells for vapor and liquid samples. 336 4. Solid samples. 337 II. Interpretation of infrared spectra 338 "" I. General 338 ;.lit," and frequencies 341 f 3 343 .1 4. Comparison of ~ "cc -_.spectra. 344 III. General features of infrared spectra of organic compounds 345 ;1' I. Paraffin hydrocarbons 345 2. Cycloparaffins 347 3. Olefins; bands associated with the carbon-carbon double bond. 348 . 4. Conjugated carbon-carbon double bonds. 354 5. Alkyl-benzenes; bands of aromatic ring systems. 356 6. Acetylenes. 361 7. Alkyl halides; the carbon-chlorine stretching band. 361 8. Alcohols, phenols and ethers 362 9. Amines, mercaptans and sulfides 364 10. Carbonyl compounds 364 a) Aldehydes. 367 b) Ketones. 367 , c) Carboxylic esters "., , 36g d) Carboxylic acids. , 370 e) Salts of carboxylic acids 370 f) Acid halides. 371 g) Acid anhydrides 371 h) Amides of carboxylic acids 371 II. Carbonic acid derivatives 373 12. Compounds containing carbon-nitrogen double tonds 373 13.. Nitriles , 373 14. Nitro c{)mpounds ,373 15. Sulfones.,a~d sulfonates ; 37f 16. More complicated structures 374 IV. Applications tQ structure determinations. 374 Penicillin : 376 V. Conclusion. 379 References. 380 Namenverzeichnis. Index of Names. Index des Auteurs. ,.. .381 Sachverzeichnis. Index of Subjects. Index des Matieres. 400 lnhal tsverzeichnis. Contents. -Table des matieres. J Some Biochemical and Nutritional Aspects in Fat Chemistry. By H. J. DEUEL, JR. and S. M. GREENBERG, Department of Bio- chemistry and Nutrition, Universityof Southern California, Los Angeles. I J. Introduction. 2 I. General Remarks on Fat Composition 2 a) Non-solvent Crystallization 4 b) Crys:t3.l1iiation from Solvents 4 c) Fractional Distillation 5 d) Chromatographic Separation 5 e) Counter current Distribution 6 f) Ultraviolet Spectroscopy 6 g) Raman Spectroscopy 6 h) Determination of Triglyceride Structure. 6 2. Composition of Substances Associated with Triglycerides 10 3. Factors Influencing the Composition of Fats. 12 II. Nutritional Evaluation of Fats in General 4 I. Functions of Fat in the Animal 4 2. The Digestibility of Fats 14 a) The Digestibility in Man of Vegetable and Animal Fats with Melting Points Below 5OoC 15 b) The Digestibility in Man of Vegetable and Animal Fats with Melting Points Above 50oC 16 c) Digestibility of Oleomargarines 18 d) Digestibility of Polymerized Oils 18 e) Digestibility of Fats in Animals Other than Man. 19 f) Factors Influencing the Digestibility of Fats. 21 .g) Utilization of Fats Introduced Parenterally 23 3. The Rate of Absorption of Fats from the Gastrointestinal Tract ...23 4. Fats as Sources of "Essential" Fatty Acids. ~ 26 5. Fat-Vitamin Interrelationships 32 a) Thiamin and Fat. 32 b) Riboflavin and Fat 34 c) Pantothenic Acid and Fat 34 d) pyridoxine (Vitamin Be) and Fat 35 - IV Inhaltsverzeichnis. -Contents. :.- Table des matiere~ e) Niacin, Folic Acid, and Fat 36 f) Biotin arid Fat. 36 g) Fat-soluble Vitamins and Fats 38 6. Relation of Fat to ~otein Metabolism. , 39 7. Fats in Relation to Specific Dynamic Action of Foodstuffs. 41 8. Fats in Relation to Growth 43 9. Fats in Relation to Sexual Maturity ; 45 10. Fats in Relation to Pregnancy and Lactation. 45 II. Fats in Relation to Work Capacity and Sur,:ival. 47 12. Fats as Antithyrotoxic Agents 49 13. Optimum Fat Levels in the Diet 50 III. Comparison of the Nutritional Value of Animal and Vegetable Fats. ...51 I. General Remarks ~~ 51 2. The Comparative Amounts of Vitamins and Essential Fatty Acids in Animal and Vegetable Fats : 52 a) Vitamin A and Provitamin A .52 b) Vitamin D 53 c) Vitamin E 54 d) Unsaturated Fatty Acid Content in Animal and Vegetable Fats. .54 3. Comparative Digestibility and Absorption of Animal and Vegetable Fats 57 4. Growth Tests with Vegetable and Anima1. Fats 57 a) Experiments with Normal Rats 57 b) Experiments on Prematurely-Weaned Rats. 61 c) Comparative Effectiveness of Animals Receiving Fats in a Restricted . Diet 62 d) Experiments on Rats Using Growth Hormones. 62 e) Growth and Nutrition Experiments °~ Children 63 5. Pregnancy and Lactation Performance of Rats Receiving Animal and Vegetable Fats 63 6. Growth and Reproduction of Rats over Many Generations on a Diet Containing a Vegetable Margarine 64 IV. Conclusions. 66 Referen ces. 67 Odeurs et parfums des animaux. Par E. LE.DERER, Institut de bio- I. logieDroguesIntroduction.R6leProduits 10 b)Muscd)a) c)e) f) physico-chimique,de LeLaPremieresSyntheses Syntheses l.odeuranima1esetd.excretion MuscCivettechimie civette danssyntheses dedes uti1isees la desgrands le musconecivettoneParis. regneglandes deen cycles cetonesparfumerieanimal sebacees. macrocycliques 87 88 88 .90 91 91 91 9~ 9~ 97 98 10~ lnhaltsverzeichnis. -Contents. -Table des matieres, v 20' Constitution chimique et odeur musquee des substances macrocycliques 106 3° Musc americain 106 4° Autres animaux a. seCretion musquee 110 5° Substances soufrees des Mustelides et d.autres animaux. ...:. III 6° Castoreum 112 7° Suintine 118 8° Yacarol 119 II. Concretions intestinales 120 10 Ambre gris 120 Composition chimique de l.ambre gris 121 Ambreine 123 Biosynthese de l.ambreine et formation de l.ambre gris. 128 Essais synthetiques dans la serie de l'ambreine 129 2° Bezoards i31 III. Substances odorantes de l.urine de Vertebre3 131 10 Derives de l.ionOne ~ 131 a) De l.urine de Lapin. 131 b) De l.urine de Jumentgravide 132 2° Phenols de l'urine de Jument gravide. 135 3° Acides de l.urine deJument gravide 136 4° Le5 steroides odorants 137 D. 5 ° Ivers 141 IV. Feces 142 Hyraceum 142 Conclusions. 143 Bibliographie 144 Vorkommen und biochemisches Verhalten der Chinone. Von 0. HoFFMANN-osTENHOF. I. Chemisches Laboratorium der Univ~rsita.t Wien 154 Einleitung 154 I. Natiirlich vorkommende Chinone 155 Das Vorkommen Von Chinonen im Mineralreich 155 Chinone bakteriellen Ursprunges 156 Durch Pilze erzeugte Chinone 157 Die Biosynthese Von Pilzchinonen 170 Funktionder Pilzchinone 172 DurchFlechten erzeugte Chinone 173 Von hoheren Pflanzen erzeugte Chinone. 173 Photosensibilisierende Chinone 178 Biosynthese und Funktion der Chinone hoherer Pflanzen 179 Chinone tierischen Ursprungs 193 II. Biologische Wirkungen der Chinone 201 Wirkungen der Chinone gegeniiber Mikroorganismen 201 Der Einflu6 der Chinone auf Vorga.nge bei der Zellteilung.. 209 Antimitotische Effekte 209 Muta~ene Effekte 212 ~ - VI Inhaltsve];zeichnis. -Contents. -Table des matieres. Wirkungen der Chinone auf tierische Organismen. 213 Wirkung von Ch.inonen auf Invertebraten '. 213 Wirkung von Chinonen auf Vertebraten. 214 Der m6g1iche Mechanismus einiger Chinonwirkungen. 216 Wirkung der Chinone auf Enzyme 217 SchluBbem~rkung 242 Literaturverzeichnis 224 J Cactus Alkaloids and Some Related Compounds, By L. RETI, ,.. Atanor". Compania Nacional para la Industria Quimica. BuenoS Aires. 242 I. Introduction. 243 II. Historical 244 III. Occurrence of Alkaloids inCacti 247 List of Cactaceae from WhichAlkaloids Qf Known Structure Have Been Isolated 247 List of Cactaceae Which Contain Alkaloids of Undetermined Structure 249 lv. Location of the Alkaloids in Tissues of the Cacti.. 250 V. Extraction and Isolationof Cactus Alkaloids. 250 VI. The Chemistry of the Cactus Alkaloids and Some Related Natural Bases 252 A. ,8-Phenylethylamines 252 I. ,8-Phenylethylamine 252. -2. N-Methyl-,8-phenylethylamine 252. -3. Tyramine 253. -4. Hordenine 254. -5. Candicine 255. .:c- 6. 0- Methyltyramine-N-methylcinnamide 756. -7. 3-Hydroxy-tyramine 256. -8. Coryneine 257. -9. Mezcaline 257. -IO. N-Methy1mezcaline 259. -II. N-Acetylmezcaline 259. -12. Trichocereine 259. B. Tetrahydro-isoquino1ines , '... 260 I. Anhala~ine 260.. -:-c- 2. Anha1inine 261.. -3. Anhalidine 261. - 4. Anhalonidine 261. -5. Pellotine 26I. -6. O-Methyl-d-anhaloni- dine 262. -7. Anhalonine 262. -8. Lophophorine 262. Structure and Synthesis of the Isoquinoline Bases Obtained from Anhalonium lewinii 262 Anhalonidine and Pellotine 262. -Anhalamine. Anhalidine and Anhalinine 263. -Anhalonine and Lophophorine 264. -9. Carnegine 264. -10. Sa1soline 266. -II. Salsolidine 266. -12. Corypalline 267. -13. Hydrohydrastinine 267. -14. Hydrocotarnine 267. VII. Biogenesis of the Cactus Alkaloids and rrheir Relation,ship to Other Natural Products ,... 268 VIII. PharJllaCOlogical Effects of Cactus Alkaloids and Some Related, Naturally Occurring Bases 276 Phenylethylamine, Tyramine, Hydroxy-tyramine 276. -Horde- nine 276. -Candicine 277. -Coryneine 277. -Mezcaline 277. - Trichocereine 278. -Anhalonine 279. -Anhalonidine 279. - Pellotine 279. -Lophophorine 279. -Camegine 279. -Pi10- cereine 279. -Salsoline 279. R"f"r"n""" ..: 280 Inhaltsverzeichnis; -COntents. -Table des matieres. VII J pl.ant Proteins. By J. BaNNER, California InstituteofTeGhno1ogy, Pasadena. 290 I. Introduction. ; 290 II. Proteins of Cereal Seeds ""., 291 III. Proteins of Seeds of Dicotyledenous Plants. 293 IV. The Leaf Proteins. 295 Preparation ~ 295 Properties of the Chloroplastic .Protein. , 299 The Cytoplasmic Proteins 301 Cytoplasmic Proteins of Leaves in Relation toVirus Formation. 304 V. Proteins ofTissues Other than Leaves 306 VI. Conclusion. , 307 References. 307 Progres recents en spectrochimie de fluorescence des produits biologiques. Par CH. DHERE, Universite de Geneve (Suisse) 311 I. Avant-propo$ 312 II. Hydroearbones (gllfcides) et glucosides. 313 Escorceine 313 Rutine ' 315 III. Sterols et steroides 315 Reaction de SALKOWSKI 316 Reaction de WINDAUS 3X7 Steroides a. fonctions hormonales 319 Reaction des steroides avec .1e sulfate dimethylique 319 Hormones surrenales ...: 320 Hormones sexuelles 321 Reactions speciales 322 IV. Proteines (protides) et aminoacides 323 Reactions_§peciales 325 V. Pyrimrdines, purineS et pterines 326 pyrimidines et purines 326 Pterines , 327 VI. Thiamine (aneurine), thiochrome et thiazol 331 VII. Adrenaline et adrenochrome 332 VIII. Alcaloides 333 IX. Polyphenols , 335 x. Derives de l'indol. 336 XI. Acide nicotinique et nicotylamide 337 XII. Uroerythrine (uroroseine) 338 XIII. Chlorophylles 338 XIV. Polyhydroxyanthraquinones et composes similaires 34° xv. Lampyrine , 343 XVI. Car~ene, phytofluene etvitamine A : 344 XVII. peniGilline et streptomycine 344 Appendice: La topographie spectrale dans l'excitation des fluorescences (Spectrofluorescence) 345 Bibliographie 349 Namenverzeichnis. Index of Names. Index des Auteurs.. 357 Sachverzeichnis. Index of Subjects. Index des Matieres. 372 k i ;~ lnhal tsverzeichnis. Contents. -Table des matieres. '1 Uber die Konstitution der Triterpene.Von 0. JEGER,.Laboratorium fur organische Chemie, Eidg. Technische Hochschule,. Zurich. I I. Einleitung 2 I. Einteilung der Triterpene 2 2. Bemerkungen zur Konstitutionsaufklarung 3 II. Squalen-Gruppe 5 Squalen " 5 Ambrein 5 III. Tetracyclische Triterpene. 12 I. Kryptosterin-Gruppe ".. 13 Vorkommen und Isolierung 13 Umwandlungen 13 Abbaureaktionen 13 a) Umwandlungen im Bezirke der Hydroxylgruppe 13 b) Umwandlungen im Bezirke der reaktionstragen Doppelbindurigen des Kryptosterins 13 2. Euphol und Butyrospermol " 4 3. Elemisaure-Gruppe 14 IV. Pentacyclische Triterpene ...; 15 I. fJ-Amyrin-Oleanolsaure-Gruppe 17 Nomenklatur 19 Vorkommen und Isolierung 19 Umwandlungen 21 Oleanolsa.ure 21 Echinocystsa.ure 24 Umwandlungen in den Ringen C, D und E des fJ;.Amyrins 27 Erythrodiol 3t Quillajasa.ure, GeninA, Maniladiol 31 Gypsogenin, Hederagenin 3z Sumaresinolsaure 36 lX-Boswellinsa.ure 4° SojasapogenoleA, B, C und D 4° Glycyrrhetinsa.ure 45 Siaresinolsa.ure 45 Germanicol 46 Basseol 47 ~ 2. ~-Amyrin-Ursols1lure-Gruppe 47 Nomenk1atur 48 Vorkommen und Isolierung 48 ~-Amyrin 49 Brein 57 {J-Boswellins1lure 59 Ursols1lure 59 Uvaol 60 3. Lupeol- und Heterobetulin-Gruppe 6I Nomenklatur ., 6I Vorkommen und Isolierung 6I Umwandlungsreaktionen 6I Lupeo1. 62 Betulin und Betulins1lure 65 Heterobetulin 66 4. Nicht vo1lig aufgekl1lrte pentacyclische Triterpene 66 Aescigenin ; ~ 66 Bassias1lure 67 Chinovas1lure ; 69 .t a) Dehydrierung 69 b) Sekund1lre Hydroxylgruppe und deren Umgebung... 69 c) Leicht abspa1tbare Carboxylgruppe 7° d) Ringe D und E. 7° Friede1in und Cerin 74 5. Stereochemie der pentacyclischen Triterpene 74 I. {J-Amyrin-Oleanols1lure-Gruppe 74 2. ~-Amyrin-Ursols1lure-Gruppe 75 3. Lupeol- und Heterobetulin-Gruppe. 76 Litera£urverzeichnis. 76 Konstitution, Konfiguration und Synthese digitaloider Aglykone und Glykoside. Von H. HEUSSER, Laboratorium fur organische Chemie. Eidg. Technische Hochschule. Zurich. 87 I. Einleitung 88 II. Aglykone und Glykoside bekannter Konstitution 94 I. Digitoxigenin. 94 a) Konstitutionsaufk11i.rung 94 b) Synthese von Abbauprodukten und Umwandlungen des Digitoxi- genins in Desoxy-corticosteron 97 c) Glykoside des Digitoxigenins 99 2. Uzarigenin 101 a) Konstitutionsaufk11i.rung und Synthese von Abbauprodukten des Uzarigenins 101 b) Glykoside des Uzarigenins 106 c) aUo-Uzarigenin 107 3. Gitoxigenin. 110 a) Konstitution und Synthese von Abbauprodukten des Gitoxigenins 110 b)c) Oleandrigenin Glykoside des (16-Acetyl-gitoxigenin) Gitoxigenins , ~ 4. Digoxigenin 115 a) Konstitution des Digoxigenins und Synthesevon Abbauprodukten 115 b) Glykoside des Digoxigenins 118 5. Sarmentogenin :' 118 a) Konstitution des Sarmentogenins und Synthese von Abbauprodukten 118 b) Glykoside des Sarmentogenins 120 6. Periplogenin 120 a) Konstitution. 120 b) Synthetische Arbeiten " 124 c) Glykoside des Periplogenins 126 7. Konstitution der allQ-Aglykone; allo-Periplogenin 127 a) Konfigurationsbestimmung 127 b) Glykoside des allQ-Periplogenins 129 8. Strophanthidin 130 a) KonBtitution 130 b) Synthetische Arbeiten und die Zusammenha.nge zwischen den einzelnen Strophanthus-Glykosiden 133 c) Glykosidedes Strophanthidins 134 d) allQ-Strophanthidin, Aglykon und Glykosid. 135 9. Strophanthidol, Aglykon und Glykoside , .136 . III. Glykoside und Aglykone unbekannter Konstitution. : .I36 :~ :1 I. Ouabain 13.6 2. Antiaris-Glykoside 139 3. Calotropis-Gifte l40 4. Sarverosid und die Sarmentoside A und B l42 5. Adonitoxin. , l42 6. Glykoside des Pfaffenhiitchens, EvQnymus eu'.opaea l43 7. Nebenglykoside des Oleanders l44 8. Glykoside und Aglykone von CQ'.Qnilla glauca l46 9. Tanghinia-Glykoside l48 IV. t'rbersichtstabellen 15° ~ Literaturverzeichnis 156 ; j } j Thyroxine and Related Compounds. By C. NIEMANN, Ca1ifornia Institute of Technology, Pasadena, California. 167 Introduction. 167 I. The Relation Between Structure and Thyroxine-like Activity 168 I. Halogenated Thyronines 16~ 2. Isomers of Thyroxine. 171 3. Thyroxine Derivatives 174 4. Homologs and Analogs of Thyroxine 175 5. General Remarks on Thyromimetic Activity. 178 II. The Synthesis of DL- and L-Thyroxine 179 i III. Inhibition of the Action of Thyroxine by Structurally Related Compounds 187 Re,ferences 190 ~ Penicillin and its Place in Science. By A. H. COOK, The Brewfug Industry Resear~h Foundation, Nutfield (England) 193 Introduction. 193 History of Penicillin and its Development. 194 Some Biochemical and Microbiological Asp.ects of Penicillin. 196 Penicillin Assay Methods 196 Dilution Assays. ; .196 Penicillin Standards. 197 The Cup-Plate Method 198 Other Assays. 198 Production of Penicillin 200 a) Culture media 201 b) Productive mould strairis 203 The Structure of the Penicillins : 204 Penicillin and Preparative Organic .Chemistry. 220 fJ-Lactams ; 220 Thiazolidines , 223 Oxazolones 225 The Synthesis of Penicillin 231 Concluding Remarks. 239 Reference" 240 Sennosides A and B, the Active Principles of Senna. By A. STOLL and B. BECKER, Chemische Fabrik vorm. Sandoz, Basel (Switzerland} 248 I. Historical 248 ll. General Considerations 25° rn. I!!olation of the Senna Glucosides 251 IV. Determination of the Molecular Weights of the Senna Glucosides and their Aglucones 253 V. Elucidation of the Structure of Sennosides A and Band their Partial Synthesis. , 254 I. Reductive Cleavage of the Sennosides and the Sennidins. 258 2. Investigation of the Meso-Compounds 262 3. Determination of the Position of the Anthrone Oxygen Atom. 264 4. The Relationship Between Sennoside A and Se~noside B 265 5. The Synthesis of Racemic Sennidin and Partial Synthesis of Sennosides A and B. 267 VI. Pharmacological Observations 268 Refetences 26q ,1 Some Recent Developments in the Chemistry of Antibodies. By J. W. WILLIAMS, Department of Chemistry, The University of Wisconsin, Madison, Wisconsin 27° Introduction. 27° I. Concentration and Purification of Antibodies. 271 'Fractionation bv Saltin~-Out 2'7~ Inhaltsverzeichnis. -Contents. -Table des matieres. VII Fractionation by Organic Precipitant or Extractant. 274 Purification of Antibodies 282 II. Characterization of the Antibody-Rich Protein Systems. ~'. 283 III. The Enzymatic Digestion of Serum .Globulins and the Characterization of the Cleavage Products 290 IV. Immunological Studies with the Several y-Globulins. 296 References. 300 Namenverzeichnis. Index of Names. Index des Auteurs. 306 SacRverzeichnis. Index of Subjects. Index des Matieres 316 Inhaltsverzeichnis. Contents. -Table des matieres. I The Fine Structure of Cellulose. By A. FREY-WYSSLING and K. MijHLETHALER, Pf1anzenphysiologisches' Institut, Eidg. Technische Hochschule, Zurich. I I. Plant Cell Wal1s 2 I. Identification of Cellulose 2 a) Preparation of Cell Wal1s 2 b) Reaction of Cellulose with Iodine 2 c) The Behavior of Cellulose toward Direct Dyes and Basic Dyes 3 d) Dissolution of Cellulose 4 e) X-ray Ana1ysis 4 f) The Double Refraction Test 5 2. Ontogeny of Cell Wal1s 6 a) Primary Cell Wal1s 6 b) Secondary Cell Walls 8 II. Microfibrils ; 10 I. Occurrence of Microfibri1s 10 a) Parallel Texture of Secondary Wal1s in Natural Fibers 10 b) Woven Texture of Primary Walls 13 c) Cellulose S1imes 4 j d) Bacterial Cellulose 16 2. Internal Structure of Microfibrils 18 t" a) No Visible Segmentation 18 b) Lamination. 19 c) Crista1linity 20 d) Intermicellar Spaces 23 III. Conclusions. 24 References. 24 j Bacterial Dextrans. By M. STACEY and C. R. RICKETTS, Chemistry Department, The University, Birmingham 28 I. Introduction 28 II. Historical. 28 III. The genus Leuconostoc 29 I. Classification ,' 29 2. Growth Factors 29 ~. Dextran Formation in Leuconostoc Cultures 30 ~ .~'; ~ ~ 4. Enzymic Synthesis of Dextran. . 3° VI.IV. V. Physico-chemicalDerivatives5.Structure Serologie of of of Dextrans Dextran.Leuconostoc. Studies of Dextran 31 32 33 36 2.I. ThePartial Macro Hydrolysis Molecule. , 36 37 3. Fractionation , 38 References.:VIII. VII. 4.5.ConclusionDextran UltracentrifugalAdsorption in Blood Analysis Transfusion.Studies. :. 39 40 41 43 43 I ,Sugar Phosphates. By L. F. LELQIR, lnstituto de investigaciones bio- ). Introduction.,\ VII.III. VI.IV. II. V. I. quimicas. PTeparationIsolationDeterminationHydrolysisTheMethodsTheRibosePentose PhosphorylationTheAcidPhosphorylationPhosphorylationsAlkalineInversionThePeriodateRibose-I-phosphateDesoxyribose-I-phosphate Ribose-3-phosphate.Ribose-5-phosphate AcidCoenzymatic Phosphates.Identi£icationStructurePositionBuenosHydrolysisPhosphates. 0£from Strength 0£ EstimationofHydrolysisof DuringOxidation Phosphoric 0£Natural SyntheticSugar Aires 0£ theAction0£ 0£the0£0£ 0£ FollowedHydrolysisSugar ofPhosphatesStructure SugartheAlcoholicSugartheAldose-I-phosphates Sourcesaqd Phosphates the ~£Esters Esters HemiacetalicPhosphatesPhosphatesIdentification. SomeCarbohydrate Phosphates.Anhydrides. by 0£, Hydroxyls GroupEsters. Sugar Group. at in Hydroxyl.Migration. Phosphates.the Solution.Component. ...: Alcoholic : Groups. 47 48 49 49 5° 5° 51 52 52 53 53 53 55 56 59 60 60 63 63 64 65 66 67 67 67 68 69 70 Arabinose Phosphates 70 D-Arabinose-5-phosphate 7° Xylose Phosphates 71 D-Xylose-l-phosphate 71 D-Xylose-5-phosphate 71 ~II. Hexose Phosphates 7z Glucose Phosphates. 7z (X-D-Glucose-l-phosphate (CoRI Ester) 7z p-D-Glucose-l-phosphate 74 (X-L-Glucose-l-phosphate 74 Gl1icose-z-phosphate 74 . Glucose-3-phosphate 75 Glucose-4-phosphate 75 Glucose-5-phosphate 76 Glucose-6-phosphate (ROBISON Ester) 76 Glucose-I,6-diphosphate : 78 Galactose Phosphates : 79 (X-D-Galactose-I-phosphate 79 p-Galactose-l-phosphate ,80 Galactose-6-phosphate 80 Mannose Phosphates. 80 Mannose-I-phosphate 80 Mannose-6-phosphate 80 Fructose Phosphates 81 Fructose-I-phosphate (ROBISON-TANKO Ester) 81 Fructose-3-phosphate 8z Fructose-6-phosphate (NEUBERG Ester) 8z Fructose-I,6-diphosphate (HARDEN-YOUNG Ester). 8z Tagatose Phosphate. 84 D-Tagatose-6-phosphate 84 Sorbose Phosphates 84 L-Sorbose-I-phosphate 84 L-Sorbose-6-phosphate : 85 IX. Disaccharide Phosphates 85 Trehalose-monophosphate 85 Malt.ose-l-phosphate 85 Unidentified disaccharide-monophosphate 86 , X. Miscellaneous PhosphateEsters., 86 Methyltetrose-phosphate 86 Ketoheptose-monophosphate 86 References 86 j The Chemistry of Nucleotides. By G. W. KENNER, The University Chemical Laboratory, Cambridge 96 Introduction 97 I. Methods. , 98 ! I. Countercurrent Distribution 98 j VI InhaItsverzeichDis. -Contents.~ Table des matieres. 2. Ion Exchange. '. 99 3. Paper Chromatography; : 101 4. Use of Physical Properties 102 5. Periodate Oxidation ; 10Z II. Ribonucleosides 103 I. Isolation 103 2. Structure. 104 3. Synthesis 108 a) pyrimidine Nucleosides 108 b) Purine Nucleosides 109 c) Nicotinamide Nucleosides 115 d) Benziminazole Nucleosides 116 III. Deoxyribonucleosides 117 I. Isolation 117 2. Structure 118 3. Synthesis ' 118 IV. Isolation and Structure of Nucleotides 119 I. Nucleotides derived from Phosphoric Acid 119 a) Adenylic Acids. 119 b) Guanylic Acids. 122 c) Cytidilyc and UridylicAcids IZZ d) Nucleotide from Vitamin B1s 12Z e) Polynucleotides IZ2 Z. Monoa1kyl Esters of. Polyphosphoric Acids. Iz3 3. Dialkyl Esters of pyrophosphoric Acid. Iz3 a) Nicotinamide Nucleotide5" Iz3 b) Flavin Nucleotides IZ5 c) The Coenzyme of "Galactowaldenase" 1Z5 V. Synthesis of Nucleotides Iz5 I. Methods of Phosphorylation 1z6 Z. Nucleotides derived from Phosphoric Acid. 13° a) 5'-Phosphates 130 b) Z'- and 3'-Phosphates 131 c) Dialkyl Esters of Phosphoric Acid 13z 3. Mononucleotides derived from Polyphosphoric Acids ..'.. 133 4. Dinucleotides derived from pyrophosphoric Acids. 135 References. ; 1~6 Die Veilchenriechstoffe. Von H. SCHINZ, Organisch-chemisches Labora- torium der Eidg. Technischen Hochschule, Zurich. I46 Einleitung , 147 BegI:iff der Veilchenriechstoffe 147 A11gemeirier Ve,]auf der Arbeiten uber die Veilchenriechstoffe 148 I. Die Jonone. 149 Konstitution der Jonone 149 Hvn,.;..,.nna n..,. Tnnnn..- I..I In l1er. Seitenkette m~thylierte Jonofie 151 Andere Untersuchungen an den Jononen , .152 Vorkommen von Jononen und ihren Abkommlingen in ~aturprodukten 153 II. Die Irone. 155 Gewinnung des Irons 155 Arbeiten von TIEMANN und KRttGER 156 Erste Synthesen auf Grund der Formel von TIEMANN und KRttGER. ..157 ~ f Tetrahydro-iron 158 Diensynthesen auf Grund der TIEMANNschen Formel 159 r I Richtige Bruttoformel des Irons 159 Synthese eines 6-Methyl-jonons (Gemisch (¥ und fJ) 161 1 Oxydativer Abbau des Irons mit Ozon und Chromsj!,ure; Hypothese der 7-Ringstruktur des Iran&c~.." 162 ~ Ultraviolett-Spektrum des naturlichen Irons; Isomerisierungen. 164 Synthesen "ironartiger" Ketone mit 7-Ring-struktur 164 " Abbau des Tetrahydro-irons; Beweis der 6-Ring-struktur 165 Ii "I-Iron ; 169 Weitere Nachweise des "I-Irons 17° ! Argumente von NAVES und Mitarbeitern zugunsten der 6-Ring-struktur des Irons; RAMAN-Spektren 171 ~ Anwesenheit von (¥-Iron im naturlichen IrongeIriisch. 171 (¥-, fJ- und "I-Iron aus genuineri undisomerisierten Gemischen von Natur- Iron. 173 Synthese von (:J::)-(¥- und (:J::)-fJ-Iron 174 Infrarot-Spektren ~ 175 Stereoisomerie-Moglichkeiten der Irone und Hydroirone ~6 Stereoisomerie-(2,6)der Irone.; 177 1 Stereoisomerie-(21,22) der Irone 178 , Vergleich der naturlichen und synthetischen Irone 179 iii!I Dihydro-irone : 181 f Tetrahydro-irone 183 Weitere Ironsynthesen 185 Andere Arbeiten mitIron 186 III. DieVeilchenblatterolVeilchenbliitenol.Svnthesen Riechstoffe von Nonadienoldes Veilchenblatter- und Nonadienal und Veilchenbliitenols .187 .187 1 .188 f! .189 f" ! IV. Geruch und Konstitution 190 ~ . Empfindung und Charakterisierung der Gertiche. 19° Gleiche Gertiche bei Substanzen verschiedener chemiScher Konstitution 191 Geruch und Konstitution innerhalb der einzelnen Korperklassen ,.. 192 Geruch und Konstitution bei den Veilchenriechstoffen 193 v. Zur Biogenese der Veilchenriechstoffe 195 Hypothese tiber die Biogenese der Terpenverbindungen im allgemeinen. 195 Hypothesen tiber die Biogenese der Veilchenriechstoffe. 196 Literaturverzeichnis 198 (11. . , ~ VIII Inhaltsverzeichnis. -Contents. -Table des matieres. Neuere Entwick1ungen auf dem Gebiete der Flechtenstoffe. Von Y. ASAHINA, Research Institute of Natural Re~ources, Tokyo. 207 ~ Einleitung 208 I. Verbindungen der Fettreihe 20~ I. Fettsa.uren und Laktone 20~ Proto1ichesterinsa.ure, Nephromopsinsaure, NephrosterinSa.ure. Nephro. steransa.ure. Caperatsa.ure, Rocel1$a.ure 209' f Rangiformsaure 209 2. Triterpenoide 210 Zeorin 210- Leukotylin 211 Urs01sa.ure 211 3. Zuckeralkoh01e 2IZ II. Verbindungen der Benz01reihe : 2IZ I. Pulvinsa.ure-Derivate 2IZ Vulpinsa.ure, Pinastrinsa.ure, Calycin 2IZ 2. Diphenylenoxyd-Derivate 2IZ Didiymsa.ure. 2IZ Strepsi1in 213 Usninsaure 214 Usnonsa.ure 216- Dihydro-Usninsa.ure, Tetrahydro-desoxy-usninsa.ure. 216- Usn01sa.ure und Decarbusn01 217 .3. Xanthon-Derivate 2I~ Lichexanthon 2I~ 4. Depside. 220 Depside der Orcin-Gruppe 220- Lecanorba.Ure-Typus: Erythrin 220 Olivetorsa.ure-Typus: Olivetonid 222 Gyrophorsa.ure-Typus: Hiascinsa.ure. 222 Depside der .8-0rcin-Gruppe 223 Nichtexistenz der Isosquamatsa.ure 22~ Hypothamn01sa.ure 223 Barbat01sa.ure ; .224 5. Depsidone.. : 225 Grundskelett des Depsidons 225- Depsidone der Orcin-Gruppe 225- Vari01arsa.ure. 225- Psoromsa.ure 226- l¥- und .8-Methylather-salazinsa.ure 227 Chlorhaltige Depsidone 228 Diploicin. 22S Gangaleoidin 229 Pannarin 2.29 6.'Anthrachinon- und Phen~nthrenchinon-Derivate 23L Magnesiumacetat a1s Reagens fiir P01yoxyanthrachinone. 23L RhodoCladonsa.ure. 231 Thelephorsaure 23Z t ~ t Inhaltsverzeichnis. .-Content. --Table des matieres. IX I 7. Stickstoffhaltige Substanzen 232 I Pikroroccellin 232 + III. Biogenese der Flechtenstoffe 234 IV. Antibiotische Wirkung von Flechtenstoffen 238 I V. MikrochemischerNachweis der Flechtenstoffe 239 Literaturverzeichnis 239 I Lupinen-Alka1oide und verwandte Verbindungen. Von F. GALI- NOVSKY, II. Chemisches Universita.ts1aboratorium, Wien : 24.5 Jr I. Einleitung 245 II. Lupinen-Alkaloide bekannter Konstitution 246 I. Bemerkungen zur KonstitutionSaufkla.rung 246 2. Lupinin. 247 3. Anagyrin. 253 4. Spartein 254 5. Lupanin 260 6. Oxylupanin 261 ~ III. Lupinen-Alkaloide unbekannter Konstitution ,. 263 IV. Verwandte Alkaloide anderer PapilionaCeen oder Pflanzenfamilien. 264 I. Cytisin 265 2. Aphyllin und Aphyllidin 267 3. Weitere verwandte Alkaloide (fraglicher Konstitution) 268 t V. Versuche einer zell-moglichen Synthese der Lupinen-Alkaloide 269 VI. Pharmako1ogie der Lupinen-Alkaloide 271 ~ Literaturverzeichnis. : : 272 Brechwurzel-Alkaloide. Von M. PAILER, II. Chemisches Universita.ts- laboratorium, Wien 278 I. Einleitung. 278 Zur Geschichte 278 Verfalschungen. 279 Hande1ss0rten. 280 II. Zusammenha.nge der einzelnen Brechwurzel-Alkaloide 280 IlI. Emetin 281 I. Konstitution 283 i 2. Rubremetin (Dehydroemetin) 292 . 3. Technische Gewinn~ng des Emetins 296 IV. Nebenalkaloide der Brechwurzel ; 297 I. Cephaelin. 297 2. Psychotrin und O-Methylpsychotrin 298 3. Emetamin 300 V. Nachweisreaktionen der Ipecacuanha-Alkaloide. 300 ~ VI. Biogenetische Betrachtungen zur Konstitution des Emetins 301 VIII.Literaturverzeichnis.. VII. TherapeutischeSynthesen von VerwendungSubstanzen mit des Emetin-WirksamkeitEmetins 30Z 303 306 I X-Ray Diffraction Studies of Crystalline Amino Acids and Peptides. III..References.Introduction.IV. II. I. By3.Inferences2.X-Ray2.3. I.Studies TheDL-AlanineL-Threonine..8-GlycylglycineOutlineRefinement2,5-Diketopiperazine.N-Acetylglycine.Glycine R. B.Trial Analysis of COREY,ConcerningofCrystalsCrystals Structurethe of of theX-Ray CaliforniaofCrysta1sof StructureAminoProteinPeptides and Method the in InstituteAcids Structure. Generaland PATTERSON Some of Technology,Related Diagram. Compounds. Pasadena. .310 .310 .311 .312 .314 .316 .318 .318 .322 .326 .330 .330 .332 .333 .337 .339 J j Some Aspects of Enzyme Chromatography. By L. ZECHMEISTER, California Institute of Technology, Pasadena. and M. ROHDEWALD, Physiologisch-chemisches Institut der Universitat Bonn. 341 I. General Remarks on Enzyme Chromatography 34z II. Methods. 344 Exchange Adsorption 344 "Salting out" Adsorption 345 Chromatography of Enzymes on Filter Paper 345 Location of Enzyme Zones on the Column by Brushing with Color Reagents 348 The Treatment of Colored Enzymes and Colored Derivatives of Colorless Enzymes 351 !II. Chromatography as a Step in the Purification of Enzymes. 353 IV. The Resolution of Enzyme Mixtures by Partial Adsorption. 354 Amylase and Maltase 355 Lichenase and Cellobiase 355 Cellulaseand Cellobiase~ 355 Cellobiase and Salicinase 355 Gentiobiase, Salicinase and Amygdalase 356 .B-Glucosidase, ~-Galactosidase and Chitinase. 356 Chitinase and Chitobiase 356 Chitinase, Chitobiase, (X- and p-Phenyl-N-acetyl-D-glucosaminase, and Salicinase. 357 Tannase and Esterase 357 Tannase and p-Glucosidase ; 357 Phosphorylase, Phosphatase and Phosphoglucomutase 357 Dehydrogenases 358 Mono- and Diphenolase 358 Thiaminases 358 Dipeptidase and Amin<;>polypeptidase 358 Trypsin, Lipase, and Amylase 358 v. The Use of Enzymes in the Chromatographic Treatment of Other Sub- stances. 359 References. 359 Namenverzeichnis. Index of Names. Index des Auteurs. 365 Sachverzeichnis. Index of Subjects. Index des Matieres. . ..377 ~ 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+CI8 19 .8-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 Com- pounds. 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 '. - - 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 52 2. Synthesis of Vitamin A via Esters of .B-Ionyltdenecrotonic Acid. ...52 .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 57 3. Synthesis of Vitamin A via "C14-Aldehyde'.' 58 Cu-Aldehyde 60 AUylic Rearrangement ,.. 60 4. 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 90 10 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 B12 94 3° 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 antivitaminesB6 97 5° Les antagonistes de l'acide nic()tinique 98 I 6° Les antagonistes de la biotin~ 98 7° Les antisulfamides lOO ~ ~~ Inhaltsverzeicbnis.- COntents. -Table d~ matieres. V 8cr Les anti-acides f01iques '; 100 9° L.activite antisu1famide et antisu1fone de derives voisins ~ l.acide p-aminobenzoique :' 101 II. Les antagonistes des vitamines lipos01ubles 102 . t .. t . I ° L an IVl amme A 102 2° Les antivitamines E 103 3° 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. 119 2. The Structure of Lysergic Acid ; 122 3. Structure of the Peptide Portion 134 III. The Individual Alkaloids of Ergot , 49 I. Ergobasine and Ergobasinine 49 2. Ergotamine and Ergotaminine : 153 3. Ergosine and Ergosinine 155 4. Alkaloids of the Ergotoxine Group 156 5. Ergocristine and Ergocristinine 159 6. 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 164 2. 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 ent- haltende Pflanzen : 179 Berberidaceae 179. -Anonaceae 179. -Magnoliaceae 179. - Monimiaceae 179. r:. Tn r,1r"r.. ..nth"lt..n.. R;,."oclaurin-Alkaloide : 179 ~ 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) I80 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 HoFMANN- schen Abbauproduktes , I81 2. Ozon-Spaltungvon Methinbasen I82 3. Aufspaltung durch Natrium in fltissigem Ammoniak 184 V. Spezieller Teil : 186 I. :5enzylisochin01in-Typus ; I86 Coclaurin 186. -Isococlaurin 187. -Magnocurarin 187. -'- Salicif01in- chlorid 188. 2. Phenanthropyridin-Typus 188 Sinomenin 188. -Disinomenin 188. -Tuduranin 189. -Step~a- nin I89. -Crebanin 189. -Phanostenin I90. -Dicentrin I90. 3. :5erberin-Typus I90 :5erberin I9°. -Palmatin I90. -C01umbamin I90. -Jatrorrhi- zin I90. -Sinactin I9I. ~ 4. :5enzochin01izin-Typus I9I Rotundin I91. 5. :5iscoclaurin-Typus. 1;92 Gruppe I. Dauricin I92. -Magn01in I92.. -Magn01amin 192. - Aztequin I93. Gruppe IIa. :5erbamin I93. -Isotetrandrin I94. -Tetrandrin I94. - Phaeanthin I95. -Cepharanthin I95.. -Oxyacanthin I95. -Re- pandin I97. -Daphnandrin I98. -Daphn01in (Trilobamin) I98. - Arom01in I98. -Epistephanin I99. -Hypoepistephanin 199. Gruppe IIb. .IsoChondodendrin I99. -Cycleanin 200. -Protocu- ridin 200.. -Neoprotocuridin 20I.. -:5ebeerin20I. -Chondro- f01in 202. -Tubocurarinch10rid 202. -ChondoCUrin 202. Gruppe lIIa. Trilobin 203. -Isotrilobin 204. -Menisarin 204. -Nor- menisarin 204. -Micranthin 205. Gruppe IIIb. Insularin 205. 6. Strukturell ungekla.rte :5asen 207 7. Optische Isomerie der :5iscoclaurin-:5asen 2°7 8. Charakterisierung der :5isc6claurin-:5asen. 209 VI.. :5iogenetische :5etrachtungen tiber :5iscoclaurin-:5asen 209 VII. Medizinische Anwendungen , 2[3 Literaturverzeichnis ..., 214 , 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 242. -Dihydro-coumarin 243. -Umbelliferone 243. - Het:~iarin 243. -Aesculetin244. -Scopoletin 245. -Fabiatrin 245. -Ayapin 245. -Citropten 245. -Daphnetin 246. -Fraxetin 247. -Fraxidin248. -Isofraxidin 249. -Fra~ino1249. -Eugenin 249. -5-Gerat;1oxy-7-methoxycoumarin 249.. Suberosin Z5°. - Collinin 250. -Brayleyanin 25°, -Umbel1iprenin 251. -Toddalo- lactone 251; -Aculeatin 252. -Auraptene 252. -Ostruthin 253. - Osthenol 254. .-Ostho1254. -Ammoresino1256. -Dicoumarol 257. VI. Furanocoumarins .., , , , 257 Psoralene260. -Angelicin 261. -Bergapten 262. -Bergapto1263. - Isobergapten 264. -Xanthotoxin 264. -Xanthotoxo1265. -Sphon- din 265. -Sphondylin 265. -Isopimpinel1in 265. -Pimpinellin 266. -Isoimperat.orin 266. -Oxypeucedanin 267. -Ostrutho1267. - Imperatorin 268. -Bergamottin 269. -Phellopterin 269. -Byak- angelicol 27&. --.: Byakangelicin 27°. -Ferulin 271. -Nodakenetin 272. -Ma,rmesin 272. -Peucedanin 273. -Athamantin 275. VII. Chromeno-lX-pyrones , , , 276 Xanthyletin27i- -Seselin 278: -Xanthoxyletin 278. -Luvangetin 280. -Al1oxanthoxyletin 281. -Braylin 281. VlII.3:4'"Benzc.oumarins 282 2' :3" -Dihydroxydibenz-lX-pyrone 282. -4: 6: 4' : 6'-Dihydroxydiphenic acid dilactone 282. -El1agic acid283. -4: 4'~Dihydroxy-6:6'-dimeth- oxydiphenic 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. ...294 2. The Theory of Protein Metabolism as a Dynamic Steady State. ...294 a) Indirect Evidence. 294 b) Direct Evidence. : 297 c) Lability of Enzyme Proteins : 298 II. The Measurement of Protein Turnover. 299 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. 310 2. Net Synthesis of Protein in vitro 3I2 3. Comparison of Incorporation 0£ AmiI.1o Aci4s: in vivo and in vitro. ..313 4. Amino Acid Incorporation in Different Cell Fractions. 313 5. 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 315 7. Normal, Foetal and Tumor Tissue , 315 8. Effect of Concentration of Labeled Amino Acid on its Rate of In- corporation 3.15 9. 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. :.. 319 T. Heats and Free Energies of Formation of Some Amino Acids and Peptides (Solids} 319 2. Free Energies of Forrilation of Some Peptides in Aqueous Solution 320 3; The Effect of PH on the Free Energy Change in Peptide Formation 321 4. 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. 334 6. 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 " , , ,,;;-~-~- Inhaltsverzeichriis; ?C6ntent$. 4;;Tabledes matieres, ~ c "- - c VII. Mechanism of Amino Acid Incoryoration ihtoProtein) 343 I. Effect of Inhibiiors 343 2. Amino Acid 1ncorporation and Phosphorylation. 346 3. Heat-Stable Co-factors for Amino Acid Incorporation. 346 4. Is Amino Acid Incorporation Synthesis of Protein de novo or an Ex- change? 347 5. The Possibility of Peptides as Intermediates in Protein Synthesis. ..348 6. 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.. 365 I. Purine Nucleoside Phosphorylase 367 2. Pyrimidine Nucleoside Phosphorylase. 372 3. Trans-N-Glycosidase 372 4. Ribosidase 374 5. Phosphoribomutase 375 6. Degradation and Synth~is of Ribose-Phosphoric Esters. 316 7. Nucleoside Deaminases 378 III. Phospho-Ribosides 381 I. Preparation and Properties of Ribose-I-phosphate 38I 2. Enzymatic Synthesis (jfRibosides 382 3. Preparation and Properties of Deoxyribose-I-phosphate 385 4. Enzymatic Synthesis of Hypoxanthine Deoxyriboside 386 IV. Trans-N-Glycosidic Reactions 387 I. Non-participation of Deoxyribose-I-Phosphate in Trans-N-glycosidic Reactiong 387 2. Trans-N-Glycosidic Reactions in the Deoxyribose N~cleoside Series. .381 3.. 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 392.. -In vitro Studies with Labelled Purines 393. - Studies on the Amphibian and Echinoderm Egg 394. -Studies on Micro-organisms 394. Reference" C1""'.."'.. , 395 J Nucleosides and Nucleotides as Growth Substances for Micro- organisms. 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 - 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 Growth- inhibition. 409 3. Nucleotides in the Nutrition of Lactobacillus gayonii 410 4. 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 413 6. Vitamin B12 417 Microbiological Functions of Vitamin B12 418 Different Forms of Vitamin B12 ,.419 II. Nucleosides and Nucleotides of Desoxyribose 420 I. The Biosynthesis of Desoxyribosides :... 421 Considerations of the Mode of Formation of the Desoxyribosidic Linkage. ...: 422 2. The Growth-promoting Activity of Desoxyribosides and Desoxyribo- nucleotides. 424 a} The Specificity of Certain Desoxyribosides in Eliciting the Growth- response of Bacteria. , .424 b) The Non-specificity ofthe Natural Desoxyribosides in Promoting the Growthof Certain Bacteria, 424 3. 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 446 2. Haptens ~~9 III. Antibodies ~5 I I. Chemical Composition of Antibodies ~5I 2.. Electrophoretic Properties of Antibodies. ~5z 3. Shape and size of Antibodies 453 4. Nature of Combining Sites : ~55 5. Purification of Antibodies ~6I d~Si Inatie:re$. t~,~..?j,;ti~,XI -,Physical Nature o.f'.Antigen-AntibodyReactions 463 :i. The Properties of Specific Precipitates. 463 a) Composition. 463 b) Formation and Specificity 465 c) 'Ageing' 466 2. Thermodynamic Properties of Antigen-Antibody Reactions. 466 a) The Free Energy and Heat Changes in Antigen-Antibody Reactions 467 b) Differences in Free Energies of Combination. ; 468 3. Nature of the Force$ Involved 471 4.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. 502 - Inhaltsverzeichnis. Contents. ~ Table des matieres. Anwendungen der Dien-Synthese fiir die Erforschung von Naturstoffen. Von KURT ALDER und MARIANNE SCHUMACHER, Chemisches Institut der Universiti1t, Koln a. Rh. I A. Allgemein er Teil. Einleitung 2 I. Die philodiene Komponente 5 II. Die Dien-Komponente 8 I. Diene 8 2. Die Tri- und Poly-ene 9 3. Die En-Synthese (indirekte substituierende AddItion) I I nl. Der Retro-Dien-Zerfall 12 IV. Die Dien-Synthes~als stereochemisches Phanomen 4 I. Dien-Synth~se und freie Drehbarkeit 14 , 2. Die sterischen Auswahlgesetze : 17 .V. Dien-Synthesen mit unsymmetrischen Addenden 21 VI. Dien-Synthese und Katalyse. Addition unter Bestrahlung. Anomalien in der Betatigung phikldiener Funktionen. Glutardialdehyd als Aus- gangsmaterial zur Synthese von achtgliedrigen Ringen. 23 B. Anwendungen. VII. Synthetische Versuche zur Darstellung von Aldehyden des Cyclocitral- und Safranal.typus ' 27 Verhalten hochmethylierter Butadiene bei Dien-Synthesen. 27 VIII. Dien-Synthesen zum Nachweis von konjugierten Doppelbindungs- systemen (Thebain, Muscarufin, Spilanthol) 34 IX. Dien-Synthesen in der Reihe der Fetts~uren 36 I. Dienometrie 36 2. Si1ure von MANGOLD 36 3. IX- und fJ-Eli1ostearinsi1ure 40 4. En-Synthesen mit ().lsi1ure-methylester 43 5. Kombinierte En- und Dien-Synthesen mit Linol- und Lin<:>lens~ure 45 X. Dien-Synthesen inder Terpen-reihe 47 I. Acyclische Terpene (Myrcen und Allo-ocimen) , 47 2. Analyse und Genese der Pyronene 51 3. Dien-Synthesen mit Menthadienen 53 4. Neue Wege in di~ Reihe desm- und des p-Menthans. : 55 5. Bicyclische Terpene 56 a) Nor-bornylan, Nor-borneol, Nor-campher. 57 b} Synthesea von natiirlichen bicyclischen Terpenen. 58 c) Konfiguration der Campheralkohole 60 d) Veral1gemeinerung. Ausblick 61 6. Di-terpene 67 XI. Steroide 69 I. Charakterisierung von Ergosterin und seinen Isomeren. 6g 2. Fraktionierte .Dien-Synthesen. Vitamin D2 und Tachysterin 72 3. Darstellung oestrogener Carbons1turen. Beitr1tge zur Konfiguration von Equilenin und Oestron 75 4. Dien-Synthesen als Ausgangspunkt fiir Totalsynthesea von Steroiden 83 XII. Cantharidin-Synthese; das Cafestol 87 XIII. Dien- und En-Synthesen mit molekularem Sauerstoff 94 Ascaridol-Synthese. Zur Frage der Entstehung von aromatischen Kernen in Naturprodukten 94 XIV. Bedient sich die N atur derDien-Synthese als Aufbauprinzip ? 99 J ~~;::;::V~~::i::~ .~~ .~.~~~~;~.. .~~. ~: ~~~~: ;~l~~~~~~~ ~~~~i~~~ 101 ofBrook1yn.Brooklyn,NewYork 119 I. Introduction 119 II. Fundamental Aspects of Rubberiness 120 III. Structure a.nd Molecular Weight of Rubbery Polymers. 126 A. Natural Rubber 126 B. Synthetic Polyhydrocarbon Elastomers. 131 I. Polyisobutylene and its Copolymers. 132 2. Polybutadiene and Polyisoprene 134 3. Polychloroprene 137 4. Butadiene-Styrene Copolymers 138 5. Butadiene-Acrylonitrile Copolymers. 141 6. Synthetic Elastomers of Various Other Types. 142 a) Rubber Elastic Polyesters and Polyamides 142 b) Elastic Polyalkyl-siloxanes ,. 144 c) Other Synthetic Elastomers 145 IV. Rubbery Materials in the Condensed State. 146 A. Crystallization of Polymers 146 a) Natural Rubber , 146 b) Polychloroprene 147 c) Polybutadiene an4 Polyisoprene 47 d) Polyisobutylene 147 e) Other Rubbery Polymers 148 B. Transition Phenomena in Amorphous Polymers. 149 C. Crosslinked Amorphous Chain Networks. 153 V. Kinetic Theoryof Rubber Elasticity 154 A. Outline of the Theory : 154 B. Comparison with the Experiment 162 References. : 164 Inhaltsverzeichl1iS. -Contents. -Table des matieres. v Chimie des lipides bacteriens. Par J. ASSELINEAUet E. LEDERER, Institut de biologie physico-chimique, Paris. 170 Introduction 172 I. Proprietes generales des lipides bacteriens. 172 II. Variations de la composition des lipides bacillaires. 174 Premiere Partie. Chimie des constituants des lipides bacterien" 176 1. Substances hydroxylees 176 ~ a) Octadecanol et eicosanol 176 b~ /X-et .B-Leprosols 176 c) Phtiocerol et substances apparentees 176 II. Acides gras ramifies 178 , a:) Acide (+) methyl-6 octanoique : ~ 178 b) Acide tuberculostearique 180 c) Acide lactobacillique 18S d) Acide phytomonique : 186 e) Acides phtioiques: acides phtienoiques et acide mycolipenique-I ...188 f) Acide coryno-mycolique 194 g) Acidc coryno-mycolenique 196 h) Corynine 197 i) Acides mycoliques des Mycobacteries. 198 I. Constitution chimique. de l'acide /X-mycolique Test. 199 2. Acides .B-, y-et6-mycoliques Test 206 3. Inventaire des acides mycoliques 2°7 A. Acides mycoliques de souches humaines 208. -B. Acides mycoliques de souches bovines 211. -C. Acides mycoliques de M.phlei 212. --D. Acides mycoliques de M. smegmatis 212. .III. Biosynthese des acides gras de:s Bacteries. 213 Biosynthesedesacidesnormaux 213 Biosynthesedesacidesramifies 213 IV. Pigments lipo-solubles 217 I I. Carotenoides 217 a) Carotenoides specifiques des Bacteries. 218 I. Leprotene 218. -2. Rhodoviolascine 219. -3. Rhodopine 219. ~ -4. Rhodovibrine ;Z19. -5. Rhodopurpurine 220. -6. Flavo- rhodine 220. -7. Sarcinine et sarcinaxanthine 220.- 8. Bacterio- ruberines /X et .B 220. b) Les carotenoides de diverses especes de Bacteries 221 I. Mycobacteries 221. -2. Corynebacteries 221. -3. Actinomy- cetes 221. -4. RhodobacilIes photosynthetiques 222. -5. Sta- phylocoque~ 222. -6. Streptocoques 222. -7. Micrococcus 223. c) Biosynthese des carotenoides des Bacteries 223 r.' VI 2. NaphtoquinonesdesBact~ries 223 a) Vitamine ~ 224 b) Homologue superieur de la vitamine K1 225 c) PhtiOCOl 225 d) Role biologique des naphtoquinones des Bacteries 226 Deuxieme Partie. Composition chimique des lipides bacillaires 226 I. Mycobact~ries ; 226 a) Graissessolublesdansl'acetone 227 b) Phosphatides 229 c) Cires A 230 ~~~~:g::::::::::::::::::::::::::::::::::.::::::::::::::::::;~ f) Cires D 233 g) Autres preparations de lipo-polysaccharides complexes. iSOlees de Mycobacteries : , 233 h) Lipides fortement lies 237 i) Acides gras des diverses fractions lipidiques 237 j) Comparaison de la Composition des lipides de diff~rentes souches de Mycobacteries 239 k) Acido-resistance. 242 2. Co'.ynebacte'.ium diphthe'.iae 242 3. Lactobacillus acidoPhilus et L. a'.abinosus 245 4. Phytomonas tumefaciens 246 5.Bacilles du genre Bacillus 247 6. Brucella. 249 7. Esche'.ichia 250 8. Malleomyces mallei 251 9. Neisseriagono'.'.hoeae 252 10. Bacilles appartenant au genre Pseudomonas. 252 II. Bacilles appartenant au genre Salmonella~. ..~-.. 253 12. Azotobacte'. ch,.oococcum 253 13. Bacilles divers 254 14. Endotoxines 254 15. Membranes cellulaires 255 Troisieme Partie. Proprietes biologiques des lipides bacillaires 2,56 Bibliographie. 256 J Syntheses of Cortisone. By G. ROSENKRANZ and F. SONDHEIMER, SyntexS.A.,MexicoCity 27~ Introduction. 275 I. Syntheses of Cortisone from Bile Acids. 276 I. Conversion of Cholic to Desoxycholic Acid 277 2. Side-Chain Degradation 278 - Inhaltsverzeichnis. -Contents. -Table des matieres. VII 3. Introduction of Oxygen at C(ll) 282 a) From a ;,1ll-Ethylene by Addition of Hypobromous Acid (REICH- STEIN) : 282 b) From a C(lB) Ketone by Removal of the C(lB) Oxyge~Group from an Intermediate 11,12-Ketol (GALLAGHER) 294 c) From a ;,1ll-Ethylene or from a C(lB) Ketone by Addition of Halogen to an Intermediate ;,1ll-3 (X,9(X-Oxide (KENDALL) 299 d) From a ;,19(ll)-Ethylene by Oxidation of the 9(X,11 (X-Oxido-3(X-ol to a 3(X,9(X-Oxido-3 fJ-ol-II-one (HEYMANN and FlESER) 304 e) Froln a ;,19(ll)-Ethylene by Oxidation with Potassium Permanganate (SARETT; WALLIS) 306 ~ From a ;,17, 8 (ll)-Diene (FIESER; HEUSSER and jEGER; D]ERASSI and ROSENKRANZ) , ,... 307 4. Formation of the Dihydroxyacetone Side-chairi and Introduction of the ;,14-3-Ketone Function ,..., ,., 310 a) Method Involvirig FISCHER Rearrangement of a Dihydroxy-aldehyde (REICHSTEIN) .'...' "' !...310 b) Method Involvirig Chromium Trioxide Oxidationbf a '7 ~,20,21-triol 21-Acetate.(SARETT) 312 c) Method Inyolvirig Simultaneous Hydroxylation and Oxidation of a ;,117(BO)-21-ol Acetate (MmscHER) ,315 d) Method Involving Hydroxylationof a;,1l7 (20)-20-Cyano-21-olAcetate (SARETT) 315 e) Method InvolvirigHydroxylationof a;,1l7 (20)-2o-Bromo-21-olAcetate (WAGNER and MOORE) , 319 f) Method Involvirig Reduction of the Oxide of a ;,1l6-20-One-21-o1 Acetate (KENDALL) , 321 g) Methods for Introducirig the ;,14-Double Bond irito 4,5 fJ-Dihydro- cortisone Acetate (KENDALL) 322 h) Methods Involving the Introduction of the 17(X-Hydroxyl Group Prior to that at C(Bl) (SARETT; GALLAGHER) 324 II. Syntheses of Co~isone from Steroids with Ring C Unsubstituted. 326 I. Introduction of Oxygen at C(ll) and Side-chairi Degradation. 327 a) Method Involvirig Hydration of a ;,17-9 (X,11 (X-Oxide (TISHLER; HEUSSER and jEGER) 328 b) Method Involving Oxidation of a ;,1~,8 (ll)-Diene with Sodium Di- chromate (FIESER) , 335 c) Method Involvirig Interaction of a ;,17, 8 (U)-Diene with N-Bromo- succiriimide (FIESER) 338 d) Method Involvirig Oxidation of a ;,17, 8 {U)-Diene with Performic Acid (STORK, ROSENKRANZ and D]ERASSI) .., 338 e) Utilization of ;,18-7-Ketones (D]ERASSI and ROSENKRANZ) , , 342 f) Method Involving Chemical Reduction of a;,18-11-One (SONDHEIMER, D]ERASSI and ROSENKRANZ; TISHLER) 344 2. Formation of the Dihydroxyacetone Side-chairi and Introduction of the;,14-3-Ketone Function 345 III. Synthesis of Cortisone from Sarmentogenin. , 349 IV. Synthesis of Cortisone from Hecogeniri 351 -'-' Table des matieres. Syntheses of Cortisone 353 , I. Synthesis According to ROBINSON and CORNFORTH 353 , 2. Synthesis According to WOODWARD, SONDHEI~ER and TAUB. 356 3. Alternative Synthesis Investigated by RoBINSON'o'. 362 4. Synthesis According to SARETT 363 VI. Biochemical Syntheses of Cortisone* 366 I. Oxygenation by Means of Adrenal Glands. 366 2. Microbiological Oxygenation 369 ,VII. Syntheses of I7(X-Hydroxy-corticosterone 370 References 372 Addendum. 388 j Rauwolfia Alkaloids. By ASIMA CHATTERJEE (nee MOOKERJEE), University College of Science and Tech~ology. Calcutta. 390 I. Iritroduction 390 II. TheAlkaloidofRauwolfiacanescens 393 Rauwolscine 393 The Pharmacology of Rauwolscine 400 III. The Alkaloids of Rauwolfia serpentina. 401 Ajmaline 402 tjmalinine 404 Ajmalicine. 405 Serpentinine .., 405 Serpentine 405 Reserpine 410 Rauwolfinine. 410 The Pharmacology of Rauwolfia serpentina 413 Pharm~cology of Reserpine 413 IV. The Alkaloids of Rauwolfia vomitoria and R. obscura. 414 ~stonine 414 The Pharmacology of Rauwolfia vomitoria and R. obscura 415 V. The Alkaloids of Further Rauwolfia Species. 415 Rauwolfia caffra 415 The Pharmacology of Rauwolfine 415 '- Rauwolfia heteroPhyUa , 415 !C The Pharmacology of R.heteroPhyUa 416 c' Rauwolfia natalensis , 416 ~au1i(olfia mombasiana ' .416 ,VI. Conclusions 416 ~eferences 417 ..i. This Chapter was written in collaboration 'with A. ZAFFARONI.. ~ !" Inhaltsverzeichni$. .;..;:;<:ontents. ,Table des matierl!8. J Insecticides Occurring in Higher Plants. By ~ FEINSTEIN and M. JACOBSON , Division of Insecticide Investigations. Bureau of Entomology and P1ant Quarantine, Ul1ited States Dept. 01 A.,griculture. Beltsville. Maryland. 423 I. Introduction. ' 424 II. Nicotine and other Tobacco Alkaloids. 426 I. General Remarks 426 2. Origin of Nicotine, Anabasine and Nornicotine. ; 428 3. Insecticidal Use. 429 4. Analysis. ; 434 5. Toxicity. 435. III. Rotenone and Related Compounds 436 I.General Remarks 436 2. Chemical Structure. 437 A. Rotenone 437 B. Deguelin 439 C.. Tephrosin 440 D. Toxicarol. 44I E. Sumatrol 442 F. Malaccol 443 G. Elliptone 443 3. Insecticidal Action. 444 4. Pharmacology 445 IV. pyrethrum 447 L GeneralRemarks 447 2. Chemical Structure. 447 3. Toxicity and Phatmacology 449 4. Synthetic Products. ; 450 V. UnsaturatedI. Pellitorine Ispbutylamides ' 452 2.. Spilanthol 453 3. Affinin 453 4.. Herculin. 453 5. Sanshool-1 arid Sanshool-II 454 6. Scabrin 454 VI. Synergetic Effects 455 I. Sesamin and Related Compounds 455 2. Piperine. 456 VII. Essential Oils, Camphor, Turpentine; Fatty Oils. 457 VIII. Miscellaneous. 459 I. Ryania speciosa 459 2. TriPterygium wilfordii HOOK 460 3. Quassia 46I 4. Sabadilla. 462 5. Hellebore (Veratrum) 463 6. Larkspur. 464 7. Mamey. 464 References. 465 Namenverzeichnis. Index of Names. Index des Auteurs. 477 Sachverzeichnis. Index of Suhiect". Index des Matieres. AQA Inhaltsverzeichnis. Contents. -Table des matieres. j Starch: Its Constitution, Enzymic Synthesis and Degradation. By STANLEY PEAT, Department of Chemistry, University College of North Wales, Bangor, Caernarvonshire I I. Introduction. 2 II. Chemical Investigations 0{ the Basic Structure of Starch. 4 I. End-Group Assay 4 2. The Molecular Size of Starch 5 III. Amylose and Amylopectin 6 1. Separation. 6 2. Comparison of Properties : 8 a) Solubility 8 b) Degree of Polymerisation 9 c) Percentage of Non-reducing End-Groups ~ d) Reaction with Iodine 9 e) C~tallinity 10 3. The Amylose-Amylopectin Ratio 10 IV. Structure of Amylose 11 1.. Molecular Size. II .2. Evidence from Amylolysis 13 \ 3. Z-Enzyme 14 4. The Maltosaccharides : 16 i V. Structure of Amylopectin 18 1. Molecular Size and Degree of Branching .18 2. Nature of the Branch Link 19 3, R-Enzyme, a Debranching Enzyme 23 4. Conformation of the Amylopectin Molecule. 24 VI. Enzymic Synthesis of Starch 25 .I. Synthesispf Amylose 26 a) The Donor. 26 b) The Acceptor. 26 c) The Enzyme 29 2. The Synthesis of Amylopectin 29 a) Th~BranchingEnzyme 30 b) The Mechanism of Branching 3° c) Substrate for Q-Enzyme 31 d) Q-Enzyme, a Transglucosylase 32 e) The Acceptor 32 f) D-Enzyme. 33 References 34 ~ IV Inhaltsverzeichnis. -Contents. -Table des matieres. Neuere Ergebnisse auf dem Gebiete des Lignins und der Ver. bolzung. Von K. FREUDENBERG, Chemisches Institut der Universita.t Heidelberg. 43 I. Einleitung 43 II. Der Stoff : 44 III. Analyse und Reaktionen ; 46 IV. Abbau 49 V. Modellsubstanzen 51 VI. Optisches Verhalten 52 VII. Biosynthese des Lignins 55 VIII. Vorstufen der Ligninbildung. Die sekund~en Bausteine 60 IX. Verkniipfung der sekunda.ren Bausteine zum Lignin 64 X. Beziehu~g der natiirlichen Ligninarten untereinander und zum kiinst- lichen Lignin. ". 66 XI. Die Bindung des Lignins iIn Holze 67 XII. Der Vorgang der Verholzung 69 XIII, SchluBwort 74 Literaturverzeichnis. 75 Probleme und neuere Ergebnisse in der Vitamin D-Chemie. Von H. H. INHOFFEN und K. BRUCKNER, Organisch-chemisches Institut der Technjschen HoChschule Braunschweig 83 I. Pra.calcifer01, ein neues Isomeres in der Reihe der Bestrah1ungsprodukte des Ergosterins 83 II. Konstitution des Vitamins D2 und des Tachysterins 87 III. Zusammenfassung neuerer Einzelergebnisse aus der Chemie der Vitamine und Provitamine D ; 90 I. Neue Verbindungen des Vitamins D2 9° 2. Neuere Methoden zur Darstel1ung von Provitaminen und Vitaminen D 91 3. Neue Vitamine D und Beitra.ge zum Zusammenhang zwischen Kon- stitution und physi010gischer Wirkung 93 IV. Ozon-Abbau des Vitamins D2; zugleich ein Beitrag zur Stereochemie der Steroide 95 V. IsomeriSierung des Vi~mins D2 91 VI. Synthetische Versuche in der Vitamin D-Reihe 102 I. Modellversuche zur Darstel1ung Vitamin D-a.hnlicher Substanzen. ..102 2. Partia1synthese Von zwei neuen Isomeren des Vitamins D2. 108 3. Syntheseversuche des '.D-Hydrindan-Ringsystems .112 VII. Photodehydro-ergosterin 115 VIII. SCh1uBwort 118 Literaturverzeichnis 118 , I~1;8verzeichnis. --Contellts. ~ Table. des matieres. ,- ' V ,; ;, ; , Natiirlich vorkommende Chromone. (Mit Anhang iiDer weitere Eleb.. . ,--,- therine-Inhaltsstoffe.) Von H. SCHMID, Chemisches Institut der Uni- versitiit Zurich. 124 I I. Einleitung. 125 II. Pflanzlicher Ursprung und Isolierung der Chromone. 126 . Ammi visnaga 126. -Peucedanum Ost'.utkium 127. -Eugenia ca'.yopkyllata 127. -Eleutke'.ine bulbosa 127. -Isolierung der ! Chromone 127. III. Konstitutionsermittlung der Chromone 127 I. Allgemeine Bemerkungen 127 Abbau mit Alkali 127. -Reaktionen der 2.-stiindigen Methyl- ,. gruppe 128. -Farbreaktionen 129. -Reaktion mit Carbonyl- . reagenzien 129. 2. Spezieller Teil 129 Chromone aus Eugenia ca'.yoPkyllata: Eugeni~ 129. -Eugenitin 130. - ~ Isoeugenitin 131. -Isoeugenitol 131, -Urnlagerungen mit Jod- i wassetstoffsii11re 13~. -ChroJIion aus Peucedanu~ Ost'.~tkium: I. Peucenin 131, -Chromone aus Ammi visnaga: Khellin 'I33. - I Visnagin 134. -Visa:mminol 136. -Khellinol 136, -Kh~llolglucosid. Khellol 137. -Konstitution und U, V.-Absorptionsspektren von 'Y-Benzopyrone~ 137. -Chromon ;tus Eleutke'.ine bulbosa: Eleutherinol 138. IV. Synthese der naturlichen Chromone und verwandter Verbindungen. ..4° I. Allgemeine Bemerkungen 14° I 2. Spezieller Teil 142 Chromo~e aus Eugenia ca'.yoPkyllata 42. -Peucenin 42. -Khellin und Khellinon 43. -Khellol 146. -Visnagin. Visnagin6n und verwandte Verbindungen 47. -Isovisnagin 48. -Al10visnagin 48. -Weitere Furo- und Dihydrofuro-chromone 15°. V.Zur Biogenese der Chromone 150 VI. Pharmakologie und therapeutische Anwendung einiger Chrom(}ne. 154 Khellin 154. -Visnagin 155. -Khellol-glucosid 155. -Visammi- no1155, -Khellinol 155. -Visnagan 155. -Klinische Verwendung von Khellin 155. . VII. Z~sammenhiinge zwisch~n Kon&titution und. pharmakologischer Wirk- sariikeit von Chromonen , 156 Anhang: VIII. Weitere Inhaltsstoffe aus Eleutke'.ine bulbosa und einige damit verwandte Verbindungen 157 Eleutherol 158. -~-Sorinin und ~-Sorigenin 160. -.8-S0rinin und .8-S0rigenin 161. -Weitere nati1rliche Naphthaline 161. -EleJl. therine-chinone und Fusarubin: Eleutherin 162. -Isoeleutherin 165.. -Allo-eleutherinZusammenhiinge 166. 166, -Fusarubin -Alloiso-eleutherin 170. 166. -Konfigurative. Litera turverzeichnis ~ VI Inhaltsverzeichnis. -Contents. -Table des matieres. The Configuration of Polypeptide Chains in Proteins. By LINUS PAULING and ROBERT B. COREY, California Institute of Technology, Pasadena.California I80 Introduction. I8I r. The Dimensions of the Amide Group I82 I. The Amino Acids I82 al The Crystal Structure of L-Hydroxyproline I82 bl The Crystal Structure of DL-Serine I86 2. Simple Peptides and Related Substances. I88 a) The Crystal Structure of ~-Glycyl-glycine. I88 .b) The Crystal Structure of N.N'-Diglycyl-L-cystine Dihydrate. I9° c) The Crystal Structure of Glycyl-L-asparagine I93 d) The Crystal Structure of Glycyl-L-tryptophan Dihydrate. I95 3. The Configuration of the Amide Group. I96 a) Dimensions of the Amide Group I96 b) Effects of Resonance I99 c) Properties of N-H. ., O Hydrogen Bonds. 200 d) Estimations of Stabilization and Strain Energies. 202 II. Helical Configurations of Polypeptide Chains. 204 I. The (X Helix. , 204 2. The yHelix and Other Helixes 207 III. Sheets of Polypeptide Chains 209 IV, The Structure of Fibrous Proteins 2I3 I. The Structure of the (X-Keratin Proteins 2I5 .. a) Some Interpretatlons of the X-ray Pattern. 2I7 b) The Occurrence of the (XHelix 220 A. Synthetic Polypeptides 220. -B. The (X-Keratin Proteins 222. 2. The Structure of Silk and the fJ-Keratin Proteins. 225 3. Collagen and Gelatin 227 V. The Structure of Globular Proteins 228 References. 234 Column Chromatography in the Study of the Structure of Pep- tides and Proteins. By W. A. SCHROEDER, California Institute 0{ Technology, Pasadena, California 240 IntrQduction 24I I. The Separation of Ammo Acids and the Determination of the Amino Acid Composition. of Peptides and Proteins. 242 I. Analytical Determination of Amino Acids by Chromatography. 242 a) Separation of Amillo Acids on Starch. 242 b) Separation of Amino Acids on Ion Exchange Resins 246 c) Comparison and Discussion of Starch and Ion Exchange Methods 246 d) Application of Starch and Ion Exchange Methods to the Analysis of Peptides and Proteins , 250 ..2. Isolation of Amino Acids by Chromatography. 255 a) Method of HIRS, MOORE, and STEIN 256 b) Method of PARTRIDGE and Collaborators. 258 c) Miscellaneous Isolative Methods 260 3. Conclusions 260 . InhaltsverzeichDjs. -Contents. -Table des matieres. VII . II. The Deter~ination of Amino Acid Sequence in Proteins. The Identification .. ~ _. of Terminal Residues and the Separation and Identification of Peptides 261 I. Identification of N-Terminal Amino Acids. 262 a) SANGER'S Method: The Use of 2.4-Dinitrofluorobenzene 262 b) EDMAN'S Method : The Use of Phenylisothiocyanate. ~69 c) Other Methods , : 271 d) Conclusions ' 271 2. Identification of C-Terminal Amino Acids 272 a) The SCHLACK and KUMPF Method 272 b) The Carboxypeptidase Method 274 c) Reduction Methods 275 d) The Flydrazinolytic Method 275 e) Conclusions. 276 3. The Separation and Identification of Peptides 276 a) The Separation of Free Peptides 277 b) The Separation of DNP-Peptides 281 .c) The Identification of Peptides 282 'd) Conclusions. 282 III. The Separation and Purification of Proteins. 283 IV. Concluding Remarks 287 References 288 Porphyrins in Nature. By R. LEMBERG, Institute of Medical Research, The Royal North Shore Flospital, St. Leonards, Sydney. 299 I. Introduction. 300 II. The Structure of the Porphin Nucleus. 301 III. The Naturally Occurring Porphyrins 306 IV. Methods of Isolation, Separation, Identification and Estimation. 310 Isolation of Porphyrins from Natural Sources 3JO Separation 310 Solubility. 310 FlCl-Method 311 Crystallisation 311 Chromatography 311 Identification of Porphyrins 312 Absorption Spectra 312 Fluorescence Spectra 34 Estimation 34 V. Individual Porphyrins 34 Protoporphyrin '.IX" 34 Mesoporphyrin ..IX" 316 Deuteroporphyrin "IX" 316 Flaematoporphyrin .'IX" 317 Chlorocruoroporphyrin 317 Porphyrin a (Cytoporphyrin) 318 Cryptoporphyrins 320 Mono-, Di-, and Tricarboxylic Porphyrins of Unknown Structure. .320 Coproporphyrins 320 Porphyrins with five to seven Carboxyl Groups 323 VIII. lnhaltsverzeichnis. -Contents. -Table des matieres. Uroporphyrins 323 Colourless Precursors of Uroporphyrins 325 Porphyrins derived from Chlorophyll 328 VI. The Biosynthesis of Porphyrins : 329 VII. The Biosynthesis of Chlorophyll ; 336 VIII. Porphyrins are not Intermediates in the Catabolism of Haem Compounds 337 References. : , 337 The Pteridines. By ADRIEN ALBERT, Department of Medical Chemistry, The Australian National University. Canberra 350 I. Introduction. 35 I II. Simple Mono- and Di-substituted Pteridines as Models for the Under- standing of Naturally-occurring Pteridines 352 I. Solubility and Fusibility 352 2. Stability to Acids and Alkalis 355 3. Ionization; Metal-binding Properties. 356 4. Spectra 360 5. Chemical Reactions. 366 III. The Natura11y-occurring Pteridines (excluding the Folic Acid Series) ..366 I. Glossary of Synonyms , 367 2. The Xanthopterin Family: Xanthopterin, Chrysopterin. Erythropterin 367 Xanthopterin 367. -Chrysopterin 36g. -Erythropterin 36g. 3. The isoXanthopterin Family: isoXanthopterin. Ichthyopterin. Fluorescyanineand Leucopterin , 37° iso~ant.hopterin 370. .,..".Ichthyopterin 370. -Fluorescyanine 37°. -Leucopterin 371. 4. Substances closely Related to the N atura11y-occurring Pteridines : Pterorhodin. Urothion 37~ Pterorhodin 371. -Urothion 372. IV. The Folic Acid Series 372 I. The Synthesis of Pteroylglutamic Acid ("PGA") 373 2. The Occurrence and Properties of Pteroylglutamic Acid. 377 3. Conjugates of Pteroylglutamic Acid ' 380 4. Rhizopterin 382 5. The Citrovorum Factor and Leucovorin. 382 6. New Members ofthe Folic Acid Series 385 V. Substances which are Presumably Pteridines 385 VI. Chromatography and other Techniques of Isolation and Purification. .388 VII; The Physiological Action of the Natural Pteridines. 389 The Simpler Pteridines : 389 The,FolicAcid Series 391 References. 392 Namenverzeichnis. Index of Names. Index des Auteurs.. 404 Sachverzeichnis. Index of Subiects. Index des Matieres..: 422 Inhaltsverzeichnis. Contents. -Table des matieres. .j Sesquiterpenes and Diterpenes. By A. J. HAAGEN-SMIT, California Institute of Technology, Pasadena, California. I .Introduction. I I. Sesquiterpenes 3 I. Acyclic Sesquiterpene~ 3 2. Bisabolene and Cadinene Type Sesquiterpenes. 3 3. Eudesmol Type Sesquiterpenes 6 4. Elemol 8 5. Eremophilone 8 6.Iresin 9 7.AzuleneTypeSesquiterpenes 10 Synthesis and Properties of Azulenes. 12 8. Longifolene I4 9. Caryophyl1ene. , 16 10. .B-Caryophyl1ene Alcohol 17 I I. Humulene 18 I2.Cedrene 18 II. Diterpenes 20 I. Structure 20 2. Stereochemistry of the Diterpenes 23 III. The Biogenesis of Sesqui- and Diterpenes 26 Biogenesis and Nomenclature 28 References. 31 hetracyclic Triterpenes. By E. R. H. JONES and T. G. HALSALL, Department of Chemistry, The University of Manchester 44 I. Introduction. 45 II. Lanostane Type Group : 48 I. Lanosterol Group 48 Occurrence and Isolation 48 Nomenclature 5°. -Interrelationship of Lanosterol, Agnosterol and their Dihydro-derivatives 51. Structure of Lanosterol : 51 Location of the~nert Double Bond 52. -The Side-chain and Ring D 59. '. IV Inhaltsverzeichms . Conteats Thble desmatleres. Stereochemistry of Lanosterol 62 Rings A and B 62. -Rings C and D 63. -Side-chain Con- figuration 64. -Stereochemistry at C(8) and C(9) in Lanostane Derivatives 64. -Lanost-7-enol 66. Synthesis of Lanostenoi 67 2. Eburicoic Acid. 68 3. Polyporenic Acid A. 73 4. Polyporenic Acid C ; 8I 5. Tumulosic Acid (PoJyporenic Acid B) 88 .6. Pinicolic Acid A 92 7. Trametenolic Acid A 95 8. cycloArtenol 96 9. cycloLaudenol 99 III. Euphane Type Group 101 I. Euphol 10I 2. Butyrospermol I08 3. Tirucallol II2 4. Euphorbol I I4 5. The Acids of Manila Elemi Resin II6 IV. Compounds of 1Jnkno'Nn Structure I2I References. I22 Neuere Vorstellungen auf dem Gebiete der Biosynthese der Steroide und verwandter Naturstoffe. Von R. TSCHESCHE, Chemisches Staats- institut der Universitat Hamburg 131 I. Einleitung. 131 II. Steroidbiogenese mit markierten Verbindungen. 132 I. Essigsaure als Baustein 132 2. Die Rolle des Squalens 136 III. Unsere Kenntnisse der biologischen Beziehungen der Steroide unter- einander 139 I. Ein C21-Sterol als Vorstufe der Pflanzensterole mit 28 und 29 C-Atomen 139 2. Gibt es Unterschiede der Biosynthese von Steroiden bei Tieren und Pflanzen ? 44 3. Ist ein C27-Sterol obligates Zwischenprodukt bei der Biogenese al1er Steroide ? 45 4. Die C3o- und C31-Steroide I5I IV. Die Hypothesen der Steroidbiogenese '. 153 I. Squa.len-Hypothese I53 2. Isosqualen-Hypothese 155 3. Hypothese von MIESCHER I55 4. Hypothese von TSCHESCHE und KORTE. 156 5. Neue Vorstellungen , 158 V. SchluJ3betrachtung I62 Literaturverzeichnis o 162 Some Biochemical Aspects of Fungal Carotenoids. ",By F. T. HAXO, Scripps Institution of Oceanography of the University of California, La Jolla, California. :: ..~ 16Q I. Introduction 169 II. Occurrence2.I. Carotenes Carotenoid of with Hydrocarbons Carotenoids Fonnula in C40H68more Fungi. Saturated than C4oH68 171 174 175 III. 3.4.CarotenoidI. Neutral Acidicb) Interrelationshipsa) Mutant Inhibitor XanthophyllsXanthophyllsFormation Studies.Studies. of in the Fungi C4o-Polyenes , 176 177 178 178 180 183 c) Studies of Light-Activated Carotenoid Synthesis. . 184 186 IV. 2.PhysiologicalI. d) Precursors Carotenoids Temperature Roleof in the SexualStu 189 190 1Q1 V. Conclusion.2. Carotenoids as Ph9tosensitizers References 19: / The Pyrrolizidine Alkaloids. By F ..L. WARREN , Department of Chemistry, University of Natal, Pietermaritzburg, South Africa. 198 I. Introduction: Origin, Occurrence and Nature of the pyrrolizidine Alkaloids 199 NatureofthePyrrolizidineAlkaloids 201 Isolation. 205 II. The Basic Hydrolysis Products 208 Retron~ine, Platynecine and Heliotridine as Derivatives of Heliotridane. .209 The Degradation of Heliotridane 211 The Structure of Retronecine and Platynecine 213 The Structure of Heliotridine 24 Monohydroxy-methylpyrrolizidines: Trachelanthamidine andSupinidine. .215 N-Oxides: Trachelanthidine and Isatinecine 216 Syntheses of Pyrrolizidine Bases 217 Stereochemistry and Syntheses of Heliotridane, Pseudo-heliotridane and their Derivatives. 22C Trihydroxy-methylpyrrolizidine: Rosmarinecine. 222 Bases of Unknown Structure: Mikanecine, Hastanecine, Turneforcidine and Otonecine ~-,224 Summary9ftheStructuresoftheBases : 22: VI Inhaltsverzeichnis. -Contents. -Table des matieres. III. The Acid Hydrolysis Products 225 C1o-Acids ; 225 Isatinecic and Retronecic Acids 227 Senecic. Integerrinecic and Usaramoensinecic Acids. 228 Seneciphyllic and isoSeneciphyllic Acids. 23i Riddellic Acid. 233 Sceleranecic and Sceleratinic Acids. 233 Jaconecic Acid and the Neutral Lactone from Jaconine 235 C1o-Acids of Undetermined Structure 236 Senecifolic, Squalinecic. Mikanecic, Grantianic and Hastanecic Acids 236 ~ Monocrotalic and Dicrotalic Acids 236 Acids having Seven-Carbon Skeleton Structures. 240 Trachelanthic Acid. 240 Viridifloric Acid. 240 Heliotrinic Acid. 241 Lasiocarpic Acid. 243 Acid from Makrotomine 243 Acid from Trichodesmine 243 IV. The Structures of the Alkaloids 244 Alkaloids from Monohydroxy-methylpyrrolizidines 245 A. AlkaloidsofTrachelanthamidine..: 245 Trachelanthamine , 245 Viridiflorine 246 Makrotomine 246 B. Alkaloids from Supinidine 246 Supinine 246 .Base C. 246 C. Alkaloids from D-isoRetronecanol 246 Lindelofine ,. 246 Lindelofamine ~ , 246 Alkaloids from Heliotridine: Heliotrine, .Base G'. Lasiocarpine 247 C18-Alkaloids from Retr'onecine. Platynecine and Rosmarinecine 248 Retrorsine. Isatidine 248 Riddelliine 249 Senecionine 251 Integerrimine 251 Usaramoensine. 252 Platyphylline 252 Rosmarinine. 252 Seneciphylline 252 Grantianine 253 Sarracine 254 Sceleratine 254 Senecifoline 254 Alkaloids from Senecio brasiliensis 254 Monocrotaline. 254 Dicrotaline 256 TheAlkaloidsasN-Oxides , 256. V. Pharmacology (with M. E. VON KLEMPERER) 257 References , 259 - VII Paper Chromatography in the Study of the Structure of Peptides and Proteins. By E. 0. P. THOMPSON and A. R. THOMl"SON, Biochemistry Unit, Wool Textile Research Laboratories, Commonwe::\Jth Scientific and Industrial Research Organization, Melbourne. Au'1;tralia .,. , .27° Introduction. 271 I. Principles of Paper Chromatography 274 II. Paper Chromatographic Techniques 276 I. Choice of Paper 276 2. Preparation of the Material for Chromatography 277 3. Application of the Material to the Paper. 278 4.EffectofpH ; 279 5. Apparatus. 279 6. Solvents , 281 7. Drying of Chromatograms 287 8. Detection of Amino Acids, Peptides and Proteins on Paper. 288 a) General Reagents 288 b) Non;Specific Reagents ~ 290 c) Specific Colour Reactions for Some Amino Acids and Peptides ..290 III. The Determination of the Amino Acid Composition of Peptides and Proteins 292 I. Qualitative Analysis 292 2. Quantitative Analysis 294 a) Measurements Applied Directly on the Paper. 295 b) Methods Involving Elution from the Paper after Reaction with a Reagent. 297 c) Methods Involving Elution from the Paper before Reaction. 299 IV. Identification of Terminal Sequences in Peptides and Proteins. 302 I. N-Terminal Sequences 303 a) Dinitrofluorobenzene Method 303 b) Isothiocyanate Method 308 c) Other Methods.. ., 312 2. C-Terminal Sequences :.. 315 a) Carboxypeptidase Method. 315 b) Reduction Methods 319 c) Other Methods. 319 3. Conclusion. 321 V. The Determination of Amino Acid Sequences in Long Chain Polypeptides and Proteins 32, . I. Separation of Component Chains 32' . 2. Methods for the Partial Hydrolysis of Peptides and Proteins. 32: I 3. Isolation and Purification of Peptides 32f ) 4. Deduction of Polypeptide Sequence from the Structure of Lower Peptides 32:7 VI. Concluding Remarks. 32:S References .328 - VIII Inhaltsverzeichnis. -'- Contents. ~ Table des matieres. Acides amines iodes et iodoproteines. Par JEAN RoGHE et RAYMOND MICHEL, Biochimie generale et comparee, College de France, Paris. .. 349 Introduction 530 II. Les acides amines iodes 35I I. Caracteres analytiques generaux des acides amines iodes ~ 35I 2. lodot~osines etiodohistidines 352 a) lodotyrosines 352 Io L-3-Monoiodotyrosine 352 2° L-3:5-Diiodotyrosine 353 b) .Iodohistidine~ 355 c) Reaction d.ioduration de laL-tyrosine, de la L-histidine et de leurs 3. lodothyroninesb)Derivesc)a) 2°Derives4Iu3°3°derives.2° lodothyronines Io ° DerivessubstituessurlephenolThyroxine.ModificationTriiodothyroninesDerivesMonoiodothyronines.Diiodothyronines de de la substituesla et thyroninethyronine derives. de la surliaison avec ; les modificationsentrenoyaux. le3 deux de noyauxla chatne laterale. . .356 .358 .359 .360 .361 , 362 .363 .364 .364 .366 .367 .367 A . 2°AcidesIo Acides amines et derives : .367 368 d { .{ 1131 4. b)a) c1esamm"smarqu"spar lodothyi-onineslodotyrosines marquees. marQuees. , 371 371 .372 III. lodoproteinesI. Proteinesb)a) Formationloduration artificiellement dedes thyroxineproteines iodees au et reactionscours .: de l.iodurationde substitution. des proteines . .373 .374 .374 .378 c) Mecanisme chimique de formation de la thyroxine et de la 3 : 5 : 3' Biblio~raphie. 2. 3. Thyroglobulineb)c)a) Scleroproteines a)b) triiodothyroninelodeProprietesPreparation. GorgoninesSpongines et acides et etlodees compositionamines antipathines iodes en acides , amines : 381 383 383 386 389 390 391 396 .jn'. J Chemistry and Biochemistry of Snake Venoms. By KARL SLOTTA, Caixa Posta14790, sao Paulo, Brazil 406 I. Introduction. ; P7 II. Snakes and Venoms 409 I. Zoological Classification of Poisonous Snakes. 409 2. Poison Apparatus .I2 3. Extraction of Venom 4I3 4. Drying and Conservation of Venom 44 III. The Action of Venoms 4 I. Pharmacological Activity 4I4 a) "Curare" Group 4I5 b) Circulation Group. 416 c) Hemorrhagic Group .I7 d) Toxic Value. 4I7 2. EnzymicActivity 4I9 IV. EJlzymesfromSnakeVenoms ~ 4z0 I. Esterases 420 a) Phospholipase A(LecithinaseA) 20 b) Phospholipases Band C 422 c) Phosphoesterases 422 d) 5-Nucleotidase 424 e) Adenosine triphosphatase(ATPase) 4z5 f) Ophio-cholinesterase(OChEase) 426 2. Carbohydrases: Hyaluronidase 426 3. Proteases 427 a) Proteinases 427 b) Peptidases 428 c) Proteolytic Enzymes and Coagulation. 428 4. Oxidases. 429 a) Catalase .29 b) Ophio-L-Amino Acid Oxidase (OAAO) 3° 5. InhibitingEnzymes 43I V. Separation, Purification, and Crystallization of Biologically Active Venom Constituents 433 I. Non-proteins , 433 2. First Attempts to Separate Active Proteins. 433 3. The Active Principles from Naia Venoms. 435 a) Neurotoxin. 435 . b) Constitution of NeurotoxiIJ 437 c) Hemolysin. 439 d) Properties and Composition of Crystalline Hemolysin 440 e) Cholinesterase 44I f) Cardiotoxin 44I g) Inhibitor. 442 4. NeurotoXin from Bunga1'us fasciatu.. Venom. 443 ~~ - x Inhaltsverzeichnis. -'-- Contents. -'-- Table des matieres. 5 The Neurotoxic and CoagulatingPrinciples from Vip/Jra russ/Jllii Venom ..443 6. Active Proteins from CrQtalus t. t/Jrrificus Veno~ 444 a) Coagulin. " 444 b) Preparation of Crotoxin 445 c)Composition. C~enrical Properties and Homogeneity of Crotoxin ..446 d) Bio1o~Cal Properties of Crotoxin 448 e}The Structuie of Crotoxin 450 VI. Electrophoresis of Snake Venoms 451 jReferences 455 Gene Structure and Gene Action. By G. \\7. BEADLE, California Institute of Technology, Pasadena, California ; 466 Introduction. 466 The Gene as a Biological Unit 466 The Chenristry of the Genetic Material 468 Transfornring Principles 469 The Genetics of Viruse~ 47° The Structure of DNA 471 Gene Specificity 472 . r Gene Reproduction. 473 ,. Gene Mutation. 473 Gene Function. 473 Genetics of Hemoglobin Structure 475 Genes and Enzymes 476 Genes and Aromatic Amino Acids 478 Summarizil1g Discussion , 480 References. ; 482 Namenverzeichnis. Index of Names. Index des Auteurs 485 .i j , Sachverzeichnis. Index of Subjects. Index des Matieres 506 i 1 Inhaltsverzeichnis. Contents. -Table des matieres. J Infrared Spectra of N~ral Products. By A. R. H. COLE, Department of Chemistry, The University ofWestern Australia, Nedlands, Australia. ..I I. Introduction. 2 ll. Methods. 3 I. General. 3 2. Instruments. 5 a) Radiation Sources. 5 b)Cells 6 c) Dispersing Systems. 6 d)Detectors 7 e)Single-Beam ~pectrQmet~rs 9 f)Double-Beam,SpecirQmeters, II g)Diffraction Gratings 4 h) Calibration. 4 3. Sampling Techniques. i5 a)Solvents 16 b) Size of Samples. 17 c)Use of Polarized Radiation 22 III. Applications. 22 I. General. 22 a)Compound Comparison 23 b) Structural Analysis. 25 2. Steroids and Terpenoids 27 A. Steroids. 28 a)Hydroxyl Absorption 30 b)C-H Stretching Absorption 33 c)Carbonyl Absorption 35 d)Ethylenic Dotible Bonds 40 e) Methyl and Methylene Bending Vibrations. 42 f)Bands in the "Fi.ngerRIjnt Region" 45 B. Terpenoids , 48 ..{ C.Studies of Stereochemistry 53 a) Axial and EquatoriaI. Hydroxyl Groups. 53 b) ~-Bromo-ketones 56 3. Application of Infrared Spectroscopy to the Structure and Configuration References.IV. Conclusion.b)ofa) CarotenoidsMycomycin. Long-Chain Polyenes 57 57 58 60 60 ~ Gallotannine und El1agen-gerbstoffe. Von 0. TH. SCHMIDT, Organisch- III. II. I. 3.4.EinleitungE1lagen-gerbstoffe2.chemischesGallotannine:I. I. ChebulagsaureCorilagin.b)Chebulinsaure1)bersi8htHexaoxy-diphensaure.Hamameli-tannina)a) (:)c) BeschreibungChebulsaureHydrolyseZurDarste1lung3.6-Diga1loyl-glu(:ose.Neochebulinsaure GesamtkonstitutionInstitut E1lagsaure-freie mit der ("Spaltsaure"undder Wasser;optisch Universitatund Analyse I,3.6-Triga1loyl-glucoseaktivenNeochebulagsaureGerbstoffe CUHJ801J Heidelberg Hexamethoxy- und Hexabenzoxy- 70 71 71 71 72 73 80 85 89 89 91 95 95 96 97 99 diphensauren sowie der racemischen und aktiven Hexaoxy-diphen- 5. b)b)Brevifolina) c) saurenBeschreibungZusammenhangeUmwandlungSynthesenSterische und Stabilitat des Brevifolin-carbonsii.ureundin Trimethyl-brevifolinsE1lagsaure;zwischen Analyse. der aktiven Konstitution. Konstitution,.Blume"-Birdung Formen sterischem Bau und Ultra- 99 100 102 105 105 110 IV. 6.Mogliche7.3. I.2. Valoneasaureb)Dehydro-diga1lussaureZura) Zurc) violett-SpektrumAlkali-SpaltungValonea-xanthon.BeschreibungEntstehungBildung Entstehung genetische der der derund Hexaoxy-diphenoyl-verbindungenBeziehungen verschiedenenChebulsaure Analyse; Ultravioiett-Spektrum und Typen Brevifolin-carbonsaure. von hydrolysierbaren Gerb- 115 1I8 118 121 124 126 126 127 Literaturverzeichnis stoffen 129 132 Neuere Ergebnisse auf dem Gebiete der glykosidischen Herzgifte : Grundlagen und die Aglykope. Von CH. TAMM, Organisch-chemische AnstaltderUniversitatBasel 137 I. Einleitung 138 II. Die Isolierung von herzaktiven Glykosiden : 139 I. Isolierung von reinen Glykosiden und Aglykonen 14° a) Herstellung der Rohextrakte I4o b) Trennung von Substanzgemischen 142 Inhaltsverzeichnis. -Contents. -Table des matieres. v 2. Farbreaktionen 43 a) Allgemeine Farbreaktionen 43 b) Farbreaktionen fiir Cardeno1ide 44 c) Farbreaktionen fiir Bufadien01ide. :.. 145 d) Quantitative Bestimmungsmethoden 145 3. Papierchromatographie 146 a) Schwach polare Glykoside und Aglykone 46 b) Stark p01are Glykoside und Aglykone 47 III. Die Konstitutionsermittlung 47 A. Abbaureaktionen 48 a) Glykosidspaltung 48 I. Chemische Methoden.., 48 2. Enzymatische Methoden 151 b) DieKonstitution der Aglykone 152 I. Carden01ide. 153 III. Die Konstitutionsermittlung 47 A. Abbaureaktionen 48 a) Glykosidspaltung 148 I. Chemische Methoden 48 2. Enzymatische Methoden 151 ~ b) DieKonstitutionderAglykone 152 I. Cardenolide. 153 a.) Beweis des Kohlenstoffskeletts. 154 p) Abbau der Aglykone zu Atiansa.uren 155 9'r Abspaltung der Hydroxylgruppe an C(14) 156 6) Stereochemie der Substituenten des Digitoxigenins (Grund- typ XIII) undseiner Isomeren..., 157 Digitoxigenin 157. -Isogenine 158. -3-Epi-digitoxi- genin 160. -Uzarigenin 160. -Urezigenin 160. B) Stellung und Konfiguration Von zusatzlichen funktionellen Gruppen. Weitere Aglykone bekannter Konstitution 161 Acovenosigenin A 161. -Periplogenin 162. -Corotoxi- genin 163. -Corog1aucigenin 163. -Strophanthidin 163. - Strophanthid01 163. -Sarmentogenin 166. ~ II-Epi-sar- mentogenin 166. -Desarogenin 166. -Dlgoxigenin 167. - Gitoxigenin 167. -Oleandrigenin 167. -Gitaloxigenin 167. -Adonitoxigenin-Allostrophanthidin 167. 169.-16-Monoanhydro-gitoxigenin -Allo-periplogenin 169. 168. - t.) Aglykone mit teilweise bekannter Konstitution 169 Adynerigenin 169. -Neriantogenin 172. -O-Acetyl- smalogenin 173. -Xysmalogenin 173. -Tanghini- genin 175. -3-Epi-tanghinigenin 175. -Abogenin 176. - Allo-glaucotoxigenin 177- -Sarmutogenin 178. -Caudo- genin 178. -Decogenin 178. -Acetyl-caulutogenin 178. -, Sarverogenin 179. -Inertogenin 179. -Leptogenin 179. - Chryseogenin 181. -Flavogenin 181. -Antiarigenin 182. -al-Dihydro-antiarigenin 182. -Nigrescigenin 183. - J 1 Ouabagenin 183. 2.. Bufadienolide 188 a.) Beweis des Kohlenst?ffskeletts. 188 fJ) Abbau zu Atiansa.uren und einige Besonderheiten: Aglykone mit bekannterKonstitution 189 Bufalin 189. -Hellebrigenin (Bufotalidin) 189. -Telo- cinobufagin 189. -Gamabufotalin 189.. -Bufotalin 189. -Bovogenin A 189. -Bovogen01 A 189. -Scillarenin 190. -Scilliglaucosidin 190. . y} Aglykone mit teilweise bekannter Konstitution Artebufogenin 191. -Resibufogenin 192. - Marinobuf( genin 193. -Scillirosidin 193. LiteraturverzeichnisIV. TabellenB.Vorbemerkung4.3. I. 2. Cardenolide.TeilsyntheseCardenolid~GlykosldeBufadienolid-GlykosideBufadienolide zu der den Aglykone Tabellen 1-4 194 195 195 196 200 202 214 216 / Natural Tropolones and Some Related Troponoids. By TETSUO NOZOE. iI. I. FacultyNaturallyIntroduction.I. Terpenoidb)a) Occurrence.HinokitiolStudies of OccurringScience, Tropoloneson or Hinokitiol TohokufJ-Thujaplicin Tropolones University,237. -Structureand Hinokitin.Sendai, of Japan. fJ-Thujaplicin 239. 232 234 236 236 2,\6 2. 4.3. Hydroxytropolone-carboxylicb)d)a)e)d)b)Purpurogallin b)Alkaloidal c)a) a) IX,-Thujapliciny-ThujaplicinNootkatinOccurrencePuberulic StipitaticPuberulonicTheThePossibleOccurrence.Colchicine WINDAUSStructureofPurpurogallin TropolonesOccurrence Acid. Acid and asMold Acid. Formula Colchiceine Metabolitesin 248.Nature Acids -Further Experimental Evidence 249. 240 241 241 241 242 243 244 245 245 245 247 247 248 -DEwAR's Colchicine Formula 25°. -Structure of Ring B 25I. - The Tropolonic Nature of Ring C 25I. -Detailed Examination of Ring C 252. 254 d) c)e)g) f) N-Formyl-desacetyl-colchicineDemecolcine2-Demethyl-colchicineColchicosideSubstances ..1" orColchamine and " J'.'and (Lumicolchicines),3-Demethyl-colchicine. and Substance '.D" ... 254 254 254 255 256 III. TheI. Tropolones SynthesisTropolone and of.Troponoids256. Tropones -Tropolone-carboxylic Acid 257. -Tropone 257. - 256 Preparation of Tropolones from Tropones 257. . 258 2. Benzotropolones 3.4-Benzotropolone 258. -4,5-BenzQtropolone 258. -3,4,5,6- Dibenzotropolone 258.. .; Inha.ltsverzeichnis.-"-COntents. ,-- Table des JIlatieres. VII 3. Colchicine Analogs 259 a) Approach to the Synthesis 259 b) Styryl-tropolones :. 259 c) Phenylethyl-tropolones and their Ring Closure. ;0. 260 d) Phenylpropyl-tropolone and Derivatives. 260 4. Halotropones. 260 5.3- and 4-Hydroxytropones 261 6. Heterocyclic Troponoids 261 IV. Physical Properties and Fine Structure. , 262 I. General Considerations. w~ 2. Acidity and Complex Formation 262 3. UltraViolet Spectra 263 4. Infrared Spectra ; 265 5. X-Ray and ElectronDiffraction 266 6. Dipole Moments 267 7. Polarography. 267 V. Chemical Properties. 268 I. General Properties of Troponoid Rings. 268 a) Ketonic Properties 268 b) Hydroxylic Function and Methyl Ethers. 268 c) Stability and Double Bond Character. 26g d) Oxidative DegI:adation of the Tropolone Ring. 27° e) Reduction of Tropolones 272 2. Cationoid and Free Radical Reactions. 2i3 a) General Considerations. 273 b) Location of Substituents 274 c) Steric Effect in Substitution ProCesses. 277 d) Halogenation of Tropolones and 2-Aminotropones. 278 e) Benzotropolones 279 f) 3- and 4-Hydroxytropones 279 g) Free Radical Reactions. 279 3. Anionoid Substitution and Rearrangements. 279 a) General Considerations. 279 b) Alkali and Alkoxides 281 c) Ammonia and Amines 282 d) Sulfides, Mercaptides, and Cyanides. 283 e) Anionic Substitution in Strong Acids 283 f) GRIGNARD Reagents and Phenyllithium. 284 g) Rearrangements with Alkali.Hypohalites or by Perhalogenation ..284 h) Some Other marrangement Reactioris': z85 4. Formation of Azulenoid Compounds 286 a) 2-OXO-I,2-dihydro-1-Oxa-azulene 286 b) 2-OXO-I,2-dihydro-I-aza-azulene and I-Aza-azulene 286 c) 2-OXO-I,2-dihydro-I-thia-3-\lza-azulene. 287 d) 2-OXO-I,2-dihydro-I,3-diaza-azulene and I,3-Diaza-azulene 287 e) 4,5-Imidazolo-tropone and 4,5-Triazolo-tropone 287 f) Azulene. ; 288 VI. Biogenetical Problems and ConcluSion. 288 References 290 -Contents. Table des matieres. J Alkaloids Related to Anthranilic Acid. By J. R. PRICE, Division of Industrial Chemistry, Commonwealth &clentific and Industrial Research Organization, Melbourne, Australia 30Z I. Introduction. , , 303 II. Anthranilic Acid Derivatives 304 Damascenine 304 III. Simple Quinoline Derivatives 305 Echinopsine .., , 3°5 F1indersine , 305 Alkaloids of Angostura 307 Cusparine : 3°7 'Galipine 3°7 Galipoline 308 Cuspareine 308 Minor Alkaloids. 309 Alkaloids of Lunasia amara 31() Quinoline Derivatives from Microorganisms 311 Cyclopenin 311 Viridicatin 311 Ps8udomonas Metabolites 31Z IV. Acridine Alkaloids 31Z Melicopicine 313 Evoxanthine 314 Melicopine 314 Melicopidine 314 Evoxanthidine 315 Xanthevodine 315 Acronycine 315 Xanthoxoline 316 V. Furoquinoline Alkaloids 317 Simple Furoquinolines 317 Dictamnine 118 VI. FuroquinolineDimethyl-pyranofuroquinolinesQuinazoline AcronycidineMedicosmineArborineV"~;I';n..MaculineMaculosidineFlindersiamineAcronidineEvolitrineFagarineKokusaginineEvoxineEvolatineKokusagineSkimmianine Alkaloids isoPentane Ethers , 323 323 324 324 324 324 325 326 326 326 327 328 328 329 330 331 ~~2 Febrifugine and isoFebrifugine 334 Evodiamine and Rutaecarpine 337 ViI.References. Quindoline Cryptolepine Alkaloids. 339 339 340 J Recent Developments in the Chemistry and Pharmacology of Rauwolfia Alkaloids. By ASIMA CHATTERJEE and SATYESH C. P AKRASHI, University College of Science and Technology, University of Calcutta, India, and G. WERNER, Faculdade de Medicina de Ribereirao Preto, UniversidadedeSaoPaulo 346 First Part: Chemistry of the Rauwolfia Alkaloids. 348 I. Introduction. 348 II. Thlj Alkaloids of R.canescens 349 Rauwolscine. 350 The Structure of Rauwolscine 352 The Stereochemistry of Yohimbme Alkaloids. 354 Yohimbine. 354 VI-Yohimbine. 355 Corynanthine 356 {J-Yohimbine. 356 Serpine 356 Alloyohimbine 356 ~- Yohimbine. 357 3-Epi-~-yohimbine , ..357 The Stereochemistry of Rauwolscine 357 Reserpine. 359 Deserpidine (Canescine, Recanescine) 359 The Stereochemistry of Deserpidine 361 Aricine 363 Isoreserpinine 365 Reserpiline and Isoreserpiline 365 Ajmaline, Ajmalicine, Reserpinine and Sarpagme 366 Raunescine and Isoraunescine 366 Serpentine. 366 'I'-Reserpine 366 III. The Alkaloids of R.serpentina 366 Methods of Isolation. 369 Ajmaline 36g Isoajmaline 374 Ajma1inine 374 Ajmalicine 375 The Stereochemistry of Ajmalicine 375 Reserpine. 376 The Stereochemistry of Reserpine. 380 Total Synthesis of Reserpine 387 Structure-Action Relation i~ Reserpine. 387 R .. Sarpagineescmnamme (Raupine) 3390 88 Rauhimbine (Corynanthine) 390 Isorauhimbine. '. 391 - x Inhaltsverzeichnis. Contents. Table des matieres. VI.IV. V. TheThe ThebaineAlstonineRaumitoTineReserpinineYohimbine3-Epi-(X-yohimbineRauwolfinineReserpicR.ReserpilineSerpentine.SerpentinineSeredineRauvomitineSerpineSerpinine AlkaloidsA)kaloidshirsuta Acid and402. ofof Papaverine-R.Methylester F\lrtherR.vomitoriaR.heterophyUa d8nsiflora Rauwolfia and 402. R.obscura -R. Species. perakensis 402. -R. inde- 391 39Z 39Z 393 393 393 395 39& 39& 39& 399 399 400 401 401 401 40Z 40Z cora 403. -R. micrantha 403. -R. tetraPhyUa 403. -Tetraphyllin 403. -Tetraphyllicine 403. -R. sellowii 404. -Ajmalidine 404. - R. semperflorens 404. -R. caffra 405. -R. natalensis 405. -R. mombasiana 405. -R. grandiflora 405. -R. cumminsi 405. - R. verticiUata 405. -R. beddomei 405. -R. degneri 405. $econd VIII. VII. IX.XI. x. Pharmacological2.HistoricalOnI.2.ThePharmacological I. Pax:t: ,R.Alkaloidb) Individuald)RauwolscineDeserpidinea) c) the PharmacologicalTertiarycaffraTertiaryOtherQuaternary BiogenesisPharmacology Introduction Mixtures.4~2.Alkaloids, Alkaloids.Ind{)lineIndole (Canescine) Effects Effects--2."Jl'; Anhydroniumof ActiontheBases of not Alkaloidsof of the RauwolfiatheketetQjJhyUa ClassifiedR. ofRauwolfia canescensR. FurtherBases serpentina AlkaloidsChemically. 422. Alkaloids.Alkaloids.Rauwolfia Alkaloids.-3. R. Species. vonntor~ : 423. 405 408 408 40~ 409 413- 413 41j. 415 421 421 421 422 42Z -4. R. hirsuta 423. -5. R. seUowii 423. XII. Concluding { Remarks ; , ~ 423 424- References. Synthese von Peptiden. Von W. GRASSMANN und Eo'WUNSCH. Max. Einleitungll. I. Planck-InstitutTheoretischeMethodischeA. Leicht abspaltbare VoraussetzungenGrundlagen fiir EiweiB- cx-Amino-Schutzgruppen.der und Peptidsyntheseder Lederforschung, Peptidsynthese Regensburg. : 444 446 447 455 455 I. Die..Acyl-blockierung.. 455 a) Carbamids1\.ureester (Urethane) 455 (X) Der ..Carbobenzoxy-rest 455 P) Modifizierte ..Carbobenzoxy-reste.. 457 y) Weitere leicht spaltbare Urethane. 457 b) Thio-urethane 458 c) Der ..Formyl-rest 460 d) Der ..Trif1uoracetyl-rest.. 460 e) Die ..Lactam-Schutzgruppen.. 462 (X) Der 2-Nitrophenoxy-acetyl-rest 462. -P) Der (2-Nitro-4- carbomethoxyphenyl-)-glycyl-rest 463. -'Y) Der ..Ch10r- acetyl-(2-aminophenyl-)-glycyl-rest 463. f) Der ..Phthalyl-rest.. 464 g) Salze der Carbamid- und Dithiocarbamids1\.ure 465 h) Der Pyrr01idon-ring 466 j) Der P-T01u01sulfonyl-(..ToSyl'.-)-rest 467 k) Phosphatamide 468 2. Die ..Alkyl-b10ckierung.. 468 a) Mono- und Dibenzyl-aminos1\.uren 468 b) N-Trityl-aminos1\.uren 469 c) Die .,SCHIFFSchen Basen.. 471 3. Die ..Ammonsalzbildung.. 471 B. Die nachtr1\.gliche Einfiihrung der (X-Aminogruppe 472 I. (X-Halogen-acyl-verbindungen 472 2. (X-Azido-acyl-verbindungen 472 c 3. (X-l\:eto-acyl-verbindungen 472 l ., r 4. (X.p-Unges1\.ttigte Acyl-verbindungen 473 l ..' C. Leicht abspaltbare (X-Carbonsaure-Schutzgruppen... 474 i~ I. Ester und Alkalisalze 474 2. N'-Phenylhydrazide 476 3. N'-Carbobenzoxy-hydrazide 476 .AminoSauren und ihre Einbeziehung in die Syn- 477 I. 477 2. Die w-Guanidogruppe 479 3. Die heterocyclischen Ringsysteme. 481 a) Imidazole. 481 b) Indole. 482 4. Die alkoh01ischeHydroxylgruppe 482 5. Die phen01ische Hydroxylgruppe 484 6. Die Sulfhydrylgruppe 487 a) Das.,Cystin-verfahren 487 b) Das ..S-Benzylather-verfahren.. 489 c) S-Aminoacyl-derivate ..: 490 7. Die ..Thioather.. ...' 490 8. Die w-Carboxylgruppe 491 a) Synthesen mit ungeichiitzter w-Carboxylgruppe : 491 b) Synthesen mit veresterter w-Carboxylgruppe 491 ~ 9. Die primare Carbonsaureamid-gruppe 492 a) Synthesen mit ungeschiitzter -CONH2-gruppe 492 b} Nachtraglicher Aufbau der --CONH2-gruppe 492 10. Aminozucker und Phosphorsaureester. 493 III. Methoden der Peptidkniipfung 494 E. Esterkondensationen 494 1. Diketopiperazine und ihre Aufspaltung 494 2. Freie lineare Esterkondensation 494 3. Cyclische Esterkondensation 495 4. Systematische Esterkondensation 495 a) Energiereiche ,..O-Ester" 495 b) Energiereiche ,.S-Ester" 496 F. O-Acyl-halbacetale 498 G. Gemischte Anhydride aus Acylaminosaure und anorganischen bzw. organischen Sauren 499 1. Die "FISCHERSche Saurechlorid-methode" 499 2. Die ..CuRTIUSsche Azid-methode" 501 3. Anhydride der PhoSphorSaure 503 4. Anhydride der Phosphorigsaure 504 5. Anhydride der Arsenigsaure 505 6. Thiosauren 506 7. Anhydride der Schwefel- und Schwefligsaure. , 507 8. Anhydride aliphatischer und aromatischer Carbonsauren 508 9. Anhydride der Kohlensaure 510 a)Bisanhydride 510 b) Anhydride der Mono-alkyl-kohlensaure 510 10. Die N(Im)-Acyl-imidaz01e 512 11. Das "Carbodiimid-Verfahren" 513 12. Cyclische "innermo1ekulare" Anhydride ~.. 5r4 a) Die N-Carbonsaure-anhydride (Oxaz01id-2.5-dione) 514 b) Die Mercapto-thiaz010ne (Thio-thiazolidone) 521 c) Oxazo10ne und "Azlactone" 522 d) N-Acyl-oxazo1idone 524 e) Spezielle innermo1ekulare Anhydride. 524 H. Energiereiche "N-Derivate" der Aminosaureester 527 I. N-Carbonyl-aminosaureester ((X-Isocyanat-fettsaureester) 527 2. Phosphatamide 528 3. N-Phosphorigsaure-derivate (Phosphitamide. -imide und PhoS- phorazokorper} 529 4. Arsenitamide 536 J. Spezielle Umlagerungsreaktionen 536 1. Symmetrische ~-Trifluoracetyl-aminosaureanhydride 536 ~. O-((X-Aminoacyl)-salicylsauren bzw. -amide. 537 Literaturverzeichnis 537 Namenverzeichnis.Sachverzeichnis. Index Index of of Subjects. Namex. IndexIndex desdes Matieres. Auteurs. .'. 560 ,83 .t : , Inhaltsverzeichnis. Contents. -Table des matieres. i Acetylenverbindungen im Pflanzenreich. Von F. BOHLMANN und H. J. MANNHARDT, Organisch-chemisches Institut der Technis<;h~n , III. IV. II. V. I. HochschuleBraunschweig2.4.VorkommenEinzelneVerbindungenMethoden3.I.EinleitungSynthetischeI. .DieChemischeDieWeitereAcetylenverbindungen b}a) LachnophyllumesterCarlinaoxydUltraviolettspektrenyltrarot- Composit-Cumulen der physikalischeund MethodenMethoden Konstitutionsaufkliirung. und Isolierung Ramanspektren Untersuchungsmethodenaus und I hoherenI6. Matricariaester Pflanzen (Angiosperme1i) 1 ., j ~ ;iJ 9 c} Weitere Dehydro-matricariaester C1o-Carbonsiiureester I8. aus -2,3-Dihydro-matricariaester Compositen. I9. d} Ester Matricarianol von Polyin-Alkoholen I9. -C1a-Alkohol aus Compositen. aus Carlina vulgaris 20. e}f} DasKohlefiwasserstoffe C1a-Kohlenwasserstoff Keton aus Artemisia aus Compositen 22. vulgaris -C1a-K6hlenwasserstoff aus Coreopsis 24. -Centaur Xa 25. g} Aromatische Phenyl-triin-Kohlenwasserstoff Acetylenverbindungen aus aus CoreopsisCompositen 25. -Ca- ,J 1 pil1in 27. ~ h} Anacyclin Dehydro-anacyclin 29. f i} Farbstoffe 4Ioo-Pigment aus Compositen31. i k} Inhaltsstoffe Centaur X-Verbindungen unbekannter Struktur.32. -Lachnophyl10133. I) Verbindungen Cicutoxin 33. aus -Cicutol Umbel1iferen 34. -Oenanthotoxin 35. - Oenanthetol und Oenantheton 36. m) Agropyren 38 - " ., . IV InhaJtsverZelOhnlS. -Contents; -Table des matieres. 2. Acetylenverbindungen in Fetten und fetten Olen. ; 39 a) Taririnsaure 39 b) Ximeninsaure und 8-0xy.ximeninsaure. 40 c) Acetylenfettsauren des Isanools 42 Isansaure 43. -Tsanolsaure 44. 3. Acetylenverbindungen aus niederen Pflanzen. 45 a) Mycomycin 46 b) Nemotinsaure und Ne1ll0tin 48 bdyssin und Odyssinsaure 49. c) Agrocybin 5° d) Verbind~ng~n aus ~titocy,be diatreta. 50 D.iatretiri I 50. -Diatretin 2 50. e) Verbindungen aus Polyporus anthracophilus 51 Matricarianol 51. -Matricariaester 52. -Decadien-diin- dicarbonsaure 52. f) Junipal 52 g) Verbindungen unbekannter Konstitution aus Pilzen , .53 Biformin 53. -DroSOphilin 53. -Quadrifidin 54. VI. Gedanken zur Biogenese der natiirlichen Acetylene. 55 VII. Die Bedeutung der natiirlichen Acetylene fiir die Pflanzensystematik 60 VIII. SchluBbetrachtung 62 titeraturverzeichnis : 62 Neuere Ergebnisse auf dem Gebiete der glykosidischen Herzgifte: Zucker und Glykoside. Von CH. TAMM, Organisch-chemische An- stalt der Universitat Easel. 71 I. Einleitung 72 II. Konstitution und Nachweis der Zucker. 72 III. Teilsynthese von Glykosiden 74 IV. Verkniipfung der Zucker in den Glykosiden. 76 V. Die isolierten Glykoside, ihre Aglykone und Zucker 78 I. Allgemein~ Eemerkungen zu ihrer Konstitution 78 a) Die Aglykone. ...; :. 78 Gitoxigenin .78. -3-Epi-oleandrigenin und 3-Epi-gitoxige- nin 79. -Tanghiferigenin 79. -Sarmutog~nin 80. -Caudo- genin 80. -Calotropagenin 80. -Sarverogenin 81. -Ouaba- genin 83. -Gomphogenin 85. -Diginatigenin 85. -Di-O- acetyl-englog~nin 8.'j. -Nicht aufgeklarte Aglykone und Glykoside 86. b) Die Zucker-Komponel1ten der GlykoSid~. 88 2. Physio10gischeWirksamkeit 90 3. Verhalten im tierischen Stofiwechsel 91 VI. Eotanisch~ Verteilung der herzaktiven Glykoside : 91 I. Die glykosidhaltigen Pflanzenfamilien ; ;.,' 91 c . 2. Verteilung der Herzglykoside in Pflanzenorganen ., ...'.:.:. 95 ~ lnhaltsverzeichnis.- Contents. -Table des matieres. v VII. Abbildungen , , , ..., , , , , .97 vnI. Tabellen ., , , , , , 102 I, Zucker der herzaktiven Glykoside " 0 ,. 102 2. Papierchromatographie der Zucker: RF-Werte , , .., :'. , , 104 , 3. Neue Aglykone und Glykoside. deren Konstitution vollstii.ndig oder teilweise gesichert ist, , , "",... 106 i 4. Glykoside mit unbekannter Konstitution: Carden01id- und Bufa- dienolid-Derivate...,." 0 ,., , ,"""'.. 108 a) Cardenolid-D~rivate 108, --b) Bufadienolid-Derivate I 12. 5. Botanische Verteilung der herzaktiven Glykoside und Aglykone, , , ..14 6. Chemische Einteilung der Strophanthusarten ..., , ..., , ., , , .126 Literaturverzeichnis ., , ., , , , , , ' , , ., , ..127 Photodynamisch wirksame Pflanzenfarbstoffe. Von HANS BROCKMANN, Organisch-chemisches Institut der Universitii.t GOttingen. ., ., .., 141 I. Der photodynamische Effekt..", ,..,.."" "...,.".,..,. r42 II. Durch photodynamisch wirksame Pflanzenfarbstoffe hervorgerufene Licht- .~i schii.digungen , , .143 I~ Hypericismus , 143 2. Fagopyrismus , 145 III. Photodynamisch wirksame Farbstoffe der Hype1'icum-Arte~ i45 I. Hypericin, , 1.46 Isolierung von Hypericin aus Hype1'icu~ hi1'sutum... 46 2. Konstitutionsaufklii.rung des Hypericins..o ,... 146 Spektroskopische Identifizierung des Stammkohlenwasserstoffes mehrkerniger Oxy-chinone , ~, 148 3, Synthesen des Hypericins , : , 156 Totalsynthese des Hypericins iiber I-Brom-emodin. 156 Synthese des Proto-hypericins und Hypericins aus Emodin-anthron-(9) 161 Partialsynthese des Proto-hypericins u~d :J;Iypericins aus Peni- , cilliopsin , 164 4, Pseudo-hypericin ..., , , , , , , , , , .167 Isolierung des Pseudo-hypericins ..,.." 168 Konstitution des Pseudo-hypericins. ..., , , , ...168 Pseudo-hypericin-Gehalt der zur Konsiitutionsaufklii.rung verwen- deten Hypericin-Prii.parate , ,..0,; ,.. 17° 5. Vorkommen von Hypericin und Pseudo-hypericin in Hype1'icum-Arten 171 Gesamtgehalt an Hypericinfarbstoffen , ..., ,. 171 Hypericin und Pseudo-hypericin in verschiedenen Hype1'icum-Arten 171 IV, Zur Biogenese der photodynamisch wirksamen Hype1'icum-Farbstoffe 172' I. Vorstufen des Hypericins, , , ".".. 172 Proto-hypericin , '.. 173 Hyperico-dehydro-dianthron 173 Emodin-anthron-(9) , , 174 2. Vorstufen des Pseudo-hypericins ; 174 3, Z'ur Stereochemie des Hypericins ,..,., , , 175 4. Natives Proto.hypericin und Hypericin. , ...176 ~ Pharmak010gisches ,...;:...:..., ,... 177 - VI Inhaltsverzeichnis. -CoIitents. -Table des matieres. .V.T.iterat11rverzeichnisVI. PhotodynamischZusammenfassung ZurProto-fagopyrinIsolierung Konstitution desFagopyrinswirksame des FagopyrinsFarbstoffe des Buchweizens ...177 ...178 ...179 .., 181 ...181 ...182 / Biosynthetic Relations of Some Natural Phenolic and Enolic Compounds. By A. J. BIRCH, Department of Organic Chemistry, The University of Manchester 186 I; Introduction: Historical Survey and Premises. 186 II. Biosynthesis of Phenols and Enols from Acetic Acid. 188 I. StructuralEvidence 188 2. Evidence Based on Biological Experime~t 192 3. Uses of the Hypothesis in Structure Determination. 194 III. Extensions ot the Acetic Acid Hypothesis 197 .\ I. Introduction of Oxygen, 198 j 2. Removal of Oxygen , , 198 3. Introduction of.Methyl and Isopentenyl and Related Groups. 200 The Mycins ., 202 . IV. Biosynthesis of C8-C3 Compounds 203 \ I. The Dehydroquinic Acid Route, 203 2, Lignin and its Congeners 204 3. Allyl- and Propenylbenzene Derivatives. 205 4. Flavonoids and Anthocya!:Iins 206 V. Some Other Natural Phenols 210 I. Terpenoid-derived Phenols 210 2. TrQpolones 211 VI. Conclusions. 212 References. 213 ,1 The Aminochromes. By HARRY SOBOTKA, NORMAN BARSEL and J. D. CHANLEY, Department of Chemistry, Mount Sinai Hospital, and International Hormones, Inc., New York. 217 I. Chemistry. 217 Introduction. 217 Structure and Preparation 219 Spectra 223 Optical Activity : 223 Pathway of Formation 224 Halogenation. 227 Rearrangements 228 Reduction. 231 Oxidation. 233 Aminochrome neriv"tiveB : 233 i - Inhaltsverzeichnis. -Contents. -Table des matieres. VII II. Physiology and Phar~acology 235 Induction of Hypoglycemia 236 Hallucinogenic Effects ; 236 Antipressor Effects ~ 236 Hemostatic Action ' 237 Therapeutic Use of Some Derivatives 238 Conclusion. 238 "23q Visual Pigments. By R. A. MORTON and G. A. J. PITT, Department of Biochemistry. TheUniversityofLiverpool 244 I. Introduction ,.. 245 Rods andCones 245 Early Work on Visual Purple 246 PioneerWorkofHECHT ,..247 RodandConeVision ,..249 The Electrophysiological Approach. 25° Acceptable Criteria for Visual Pigments. 252 II. Vitamin A 253 Discovery and Preparation of Retinene. 254 VitaminA2 and Retinene2 255 III.. Cis-trans Isomerism ofRetinenel 257 SynthesisofIsqmers 359 Properties 9f Isomeric Retinenes and Vitamins A 263 IV. Rhodopsin. 265 PreparationofRodOuterSegments 266 ExtractionofRhodopsin 267 Contaminants in Rhodopsin Solutions. 268 PurityofRhodopsinPreparations 27° Transient Orange and Indicator Yellow. 273 Lumi- and Meta-rhodopsin 275 N-Retinylidene-opsin 279 Retinene-Opsin Linkages 281 SpectrosCopic Considerations 285 V. Porphyropsin 287 Visual Pigments of Fish 288 Visual Pigments of Xenopus 293 VI. Other Retinenel-Pigments 295 VII. Cone Pigments. 296 Iodopsin. : 299 Cyanopsin 304 VIII. Iso-pigments 304 IX. Visual Pigment Chromophores : 306 References. 307 VIII lnhaltsverJeichni8., -Contents. Table des mamres. j The Carbon Cycle in Nature. By HARRISON BROWN, California Institute VIII.References' VII. III.IV.IX. VI. II. V. I. of 2.2.3.TheIntroduction.3.I.Variations5.4.I.2.VariationsThe RatesI.MiscellaneousQuantitiesCarbon 2.3. I. Technology, WaterPhotosynthesisCarbon.TheEarlyPhotosynthesisRespiration'andCarbonCarbonaceousCarbonAtmosphericOrganic CyclingEvolution of ProductionDeposited ProductionPhotosynthesis inonfrom inin of Material of Pasadena,thethe ReactingtheAspects of CarbonMethane.the Chondritic UniverseCarbonIsotopic inonPrimitivethe in of OxidationinDepths of the theLand OxygenPresent: RainwaterasSi1bstancesOrganic California and Oceans SedimentsDioxide Carbonate Composition Meteorites. Earth of Carbon ChemicalOxidation. of the System. of Air Compounds.Carbon ~ .~, : 317 317 318 318 319 320 320 320 323 323 325 326 326 327 327 327 328 329 330 332 332 Namenverzeichnis. Index of Names. Index des Auteurs 334 Sachverzeichnis. Index of Subjects. Index des Matieres. 345 Inhaltsverzeichnis. Contents. -Table des matieres. Der Kohlenhydratstoffwechsel der Graser. Von H. H. SCHLUSACH, Chernisches Staatsinstitut, Universitat Hamburg. I I. Einleitung I II. Das Pf1anzenmaterial 2 III. Die Isolierun g der loslichen Kohlenhydrate 3~ IV. Die analytischen Methoden 5 V. Die Konstitution der Polysaccharide der Graser. 7 VI. Die niedermolekularen Kohlenhydrate in den Grasern. 12 VII. Die Biogenese der Oligo- und Polysaccharide der Graser 14 VIII. Abwandlungen des Kohlenhydrat- und des EiweiBgehaltes im J;.aule einer Vegetationsperiode 17 IX. Anwendungen auf die Grtinlandwirtsch;tft. 23 Literaturverzeichnis 27 j Some in vitro Conversions 0£ Naturally Occurring Carotenoids. By L. ZECHMEISTER, California Institute of Technology, Pasadena, California. 3I I. Introductory Remarks 32 normal and retro Strnctures 33. ~ Addition of Hydrogen to the .Chromophore 34. ~ Addition of Oxygen to Terminal Double Bonds of the Chromophore 35.. ~ Lengthening of the Chromo- phore 36. II. Preparation and Conversions of Carotenoids by Means of N-BromoSUccin- imide 36. I. Dehydrogenation of Colorless Compounds to Carotenoid Pigments 37 Squalene 37. ~ PhytqenE? and Phytofluene 37. 2. Action of N-Bromosuccinimide on {J-Carotene 40 a) N-BromoSUccinimide and {J-Carotene in Carbon Tetrachloride Solution. 40 retro-Dehydrocarotene 40. ~ retro-Bisdehydrocarotene 4°. ~ Anhydro-eschscholtzxanthin 41.. ~ 3,4,3',4'-Bisdehydro-{J-caro- tene AI. ~ ~.A-Dehvdro-B-carotene 42. IV b) N-Bromosuccinimide and p-Carotene in Ethanol-Containin? Chloroform Solution ; 42 Formation of Ketones 42. -4-Keto-3'.4'-dehydro..p-carotene 43. -4-Keto-p-carotene and 4.4'-Diketo-p-carotene 45. -Identi- fication of 4-Keto-p-carotene and 4.4'-Diketo-p-carotene with Natural Products 47. -Addendum 47. 3. Action ot N-Bromosuccinimide on ~-Carotene 48 3.4-Dehydro-~-carotene 48. / 4. Action of N-Bromosuccinimide on Lycopene 49 5. A<:tion of N-Btomosuccinimide on Cryptoxanthin. 49 6. Action of N:.Bromosuccinimide on Physaliene 49 rrr. Conversions of Carotenoids via their Boron Trifluoride Complexes. ...50 I. Cleavage Products of the p-Carotene-BF3 Complex. 51 2. Cleavage Products of the ~-Carotene-BF3 Complex. 52 3. Cleavage Products of the BF3 Complexes of Some Dehydrogenated Carotenes. 55 a) retro-Dehydrocarotene-BF3 55 b) 3.4-Dehydro-~-carotene-BF3 and 3.4-Dehydro-p-carotene-BFa 56 c) retro-Bisdehydrocarotene-BF3 57 4. Cleavage Products of the Lycopene-BF3 Complex. , 58 5. Cleavage Products of the y-Carotene-BF3 Complex. 60 6. Cleavage Product of the An1iydrovitamin A1-BF3 Complex. 61 IV. Dehydration and Dehydrogenation of Lutein. 62 V. Some Spectroscopic Observations ..., 63 Position of the Maxima 65. -Lengthening of the p-Carotene Chromophore 67. -Influence of the Spatial Configuration 70. -'- Transition from normal to retro Structures 73. -Spectral Curves 75. References ~~~t:~.- 16 / The Chemistry of Podophyllum. By J. L. HARTWELL and A. W. SCHRECKER, Laboratory of Chemical Pharmacology, National Cancer Institute, National Institutes of Health, Public Health Service, U. S. Department of Health, Education and Welfare, Bethesda, Maryland 83 I. History ,84 II. Preparation of Podophyllin 88 III. Composition of Podophyll4m , 88 IV. Other Sources of Podophyllum Lignans. 93 V. Isolation Plocedures 94 I. Isolation without Chromatography. 95 2. Adsorption Chromatography; 96 3. Partition Chromatography 97 VIII. VII. VI. Desoxypodophyllotoxin5.Dehydropodophyllotoxin.PodoJlhyllotoxin2.4.3.I.. ThePropertiesStereo<;:hemistrySyntheticStructure Apopicropodophyllins. Approaches. :0:'-: ..98 ..98 ..99 ..108 ..III ..119 121 123 IX. 4'-Dernethylpodophylloto~in. . 124 X. The Peltatins 126 XI. Sikkimotoxin 13° XII. Lignan Glucosides 133 XIII. Ionic Derivatives of Podophyllotoxin and of the Peltatins 136 XIV. Flavonols 138 v., 2.AbsorptionI. Infrared Ultraviolet Spectra. Spectra. .139 .139 .143 XVI. Biological Actiol1 .. 143 XVll. Tables. 145 I. Well-characterized Compounds Isolated from Podophyllum Species 45 2. Solvates and Modifications of Podophyllotoxin. 146 3. Molecular Rotations of Compounds in the Conidendrin and Desoxy- podophyllo"toxin Series 46 4. Podophyllotoxin and Derivatives. 147 5. Desoxypodophyllotoxin and Derivatives. 150 6. 4'-Demethylpbdophyllotoxin and Derivatives. 150 7. Peltatins!1nd Derivatives 151 8. Sikkimotoxin and Derivatives 152 9. Lignan Glucosides and Derivatives. 152 10. Maximum Tolerated Doses (MTD) and Minimum Effective Doses (MED) in.Mice Bearing Sarcoma37 153 II. Ionic Derivatives of Podophyllotoxin and of the Peltatins, and Intermediates 154 12. Flavonolsand Derivatives , , 155 13. Ultraviolet Absorption Maxima of Podophyllum Lignans and of Some of Their Derivatives : 156 References. I~7 ~ / X-ray Analysi~ and the Structure of Vitamin B12. By DOROTHY CROWFOOT HODGKIN, University Museum, Oxford. 167. I. Introduction , 167. II. Some Characteristics of the X-ray Crystallographic Methods Applied to the Analysis of VitaminB12 169 m. The Determination of the Structure of Vitamin B12 173 I. Preliminary Crystallographic Measurements and Observations. 173 . 2. The Stages of Atom Identification 176 a) The Cyanide Group 179 b) The "Nucleotide" Group 17.9 c) The Corrin Nucleus 183 d) The Side-chains Attached to the Nucleus. 185 e) The Propanolamine Groups 189 3. The Problem of Right and Wrong Atoms 194 4. The Refinement of the Atomic Positions. 195 5. The Absolute Configuration of the Moiecule. 196 6. The Chemical Formulae of Vitamin B12 and the Hexacarboxylic Acid 196 IV. The Chemical Reactions of Vitamin Bt2 202 V. Biochemical Problems Connected with the B12 Structure. 207 VI. The Crystal Structures of Vitamin B12 and the Hexacarboxylic Acid. ; 212 VII. Conclusion. 218 References. 218 Namenverzeichnis. Index of Names. Index des Auteurs Sachverzeichnis. Index of Subjects. Index des Matieres. Inhaltsverzeichnis. Contents. -Table des matieres. J Catechine. andere Hydroxy-flavane und Hydroxy-flavene. Von ~ARL FREUDENBERG und KLAUS WEINGES, Chemisches Institut der Uni- versita.t Heidelberg I I. Altere Arbeiten. I 2. Die bekannten Hydroxy-flavane 2 3. Eigenschaften, Herstellung der Hydroxy-flavane 5 4. l(ondensation durch sauren 5 5. Hydroxy-flavene 9 6. Leucoanthocyanidin-hydrate. Acetate der PseudoanthoCyanidine rind de.r Pseudoanth06yanidin-hydride. 12 .7. Oxydations- und Reduktionsiibergange in der C8C3C8-Reihe. 15 8. Cyanomaclurin 15 9. Catechin-3-gallat und Catechin-3-g1ucoSid. 17 10; Stereochemie der Catechine 18 II. Biogenese der C8CaC8-Gruppe 21 Literaturverzeichnis 22 j Recent Progress in the Chemistry of the Aconite-Garrya Alkaloids. By KAREL WIESNER and ZDENEK VALENT A, Department of Chemistry. The University .of New Brunswick, Fredericton, N. B., Canada. 26 I. Introduction. 27 II. Garrya Alkaloids. 28 I. The Structure of Veatchine and Garryine 28 Environment of the Nitrogen 28 Structure of the Skeleton 3I Structure of the Oxoveatchine Dicarboxylic Acids 33 StructuTe Assignment to Veatchine a:nd Garryine 35 2c The Stereochemistry of the Garrya Skeleton and its Influence on the Properties of Garrya Alkaloids 36 3. The Structure of Cuauchichicine anII: Garryfoline .: 40 4. Configuration of the Secondary Hydroxyl Group in Veatchine and Garryfoline ~ 42 ~ I.nhaltsverzeichnis. -Contents. ~ Table des matieres. III. The Structure of Atisine 44 Original Degradation Work on Atisine 44 Similarity of Atisine with the Garrya Alkaloids and the Deduction of the Atisine Structure 45 Some Confirmatory Evidence 47 IV. Biogenesis of Veatchine and Atisine and Consideration of the Stereo- chemistry of Atisine 50 V. The Structure of Ajaconine 53 VI. The Structure of Napelline 53 VII. The Chemistry of Hetisine 62 VIII. Lycoctonine and Delpheline 63 I. The Chemistry of Lycoctonine 64 Oxidation Studies 65 Skeletal Changes 69 2. The CheInistry of Delpheline 72 Environment of the Nitrogen 72 Transformations in the Demethylene Series. 74 The Carbon Skeleton of Delpheline 79 3. Biogenesis of Lycoctonine and Delpheline 80 IX. The Chemistry of Delphinine 81 References. 87 J Structural Chemistry of Actinomycetes Antibiotics. By E. E. VAN TAMELEN, Department of Chemistry, The University of Wisconsin, Madison, Wisconsin. 90 Introduction 90 I. Actidione (Cycloheximide) 92 2. Actinomycins. 93 3. Actithiazic Acid. 94 4. Amicetin 95 5. Aureomycin (Chlorotetracycline) 98 6. Aureothricin and Thiolutin 101 7. Azaserine. 102 8. Chloromycetin (ChlQramphenicol) 103 9. Cycloserine (Oxamycin) 104 10. Elaiomycin. 105 II. Erythro~ycin ; 106 12. Etamycin (Viridogrisein) 1()9 13. Magnamycin (Carbomycin) 116 4. Methymycin. 113 15. Mycomycin 115 16. Netropsin : 116 17. Nocardamine 118 18. Novobiocin. 118 19. Puromycin (Achromycin) X21 20. Sarkomycin : 123 21. Streptomycin. ., 124 22. Terramycin 128 23. Tetracycline ~3i 24. Valinomycin. L32 References. :': ~32 J Protein Synthesis in Plants. By JAMES .BONNER, California Institute of T~hnology, Pasadena. California ~39 I. Introduction. ~4O l~ i II. Isolation of Microsomes ~4° It"" " III. Structure of the Microsomes i43 IV. Role of the Microsomes in Protein Synthesis ~44 V. Biology of the Microsomes ~46 ~. NuclearMicrosomes ~46 2. Origin of Microsomes ~47 3. Transfer of Microsomal RNA ~48 4. Synthesis of the Microsomal Components. ~49 5. Kinetics of Microsomal Labeling ~5~ VI. Protein Synthesis as a Catenary Sequence. ~53 ~. Amino Acid Activation ~54 2. Transfer to Soluble RNA ~55 3. The Microsome as Acceptor of Amino Acid. ~57 4. Alternative Pathways of Peptide Synthesis. ~58 VII. Protein Synthesis in Mitochondria and Chloroplasts. ~6o VIII. Protein Synthesis in Varied Plant Organs. ~6~ ~. Developing Fruits and Seeds 16~ 2. Leaves. ~62 IX. Conclusion ~64 References. 164 J The Electron Gas Theory of the Color of Natural and Artificial Dyes : Problems and Principles. By HANS KUHN, Physikalisch-Chemisches Institut der Universitat Marburg a. d, Lahn. 169 I I. Some Experimental Facts Concerning Color and Structure.. 17° I. Polyacetylenes, Polyenes. Symmetrical Cyanine Dyes. and Some Similar Compounds. 17° 2. Aza Derivatives of Symmetrical Cyanine Type Compounds. 175 3. Acridine Type Bridge Formation in Symmetrical Cyanine Type Compounds. 176 4. Some Other Types of Resonance Systems Causing Absorption of Visible Light 178 II. Some General Principles and Postulates. 178 I. Light Quanta and the Einstein-Bohr Frequency Relation. 179 2. Wave Particle Duality of the Electron and the de Broglie Relationship 180 3. Standing Electron Waves. The Pauli Principle. : 180 4. The Chemical Bond; (1 and n Electron States. : 184 ~ III. Quantum Mechanical Determination of the Position of the Absorption Bands of Simple Dyes 190 I. A Simple Model of Symmetrical Cyanine Dyes 19° 2. A Simple Treatment of the Aza Derivatives of Symmetrical Cyanine Type Compounds 194 References. 201 Namenverzeichnis. Index of Names. Index des Auteurs. 206 sachverzeichnis. Index of Subjects. Index des Matieres. 213 Inhaltsverzeichnis. Contents. -Table des matieres. J Flavones and Isoflavones. By K. VENKATARAMAN, National Chemical Laboratory, Poonit, India I I. Introduction. 2 II. Structural Relations and Interconversions 4 III. OcGuqence in Plants. 6 Glycosides 6 Hydroxy~ation Patterns. 7 IV. Isolation ; 9 V. Color Reactions. 12 VI. Survey of Natural Flavones 14 Flavone. 5-Hydroxyflavone and Dihydroxyflavones 4 Trihydroxyflavones , 15 Tetrahydroxyflavones 16 Pentahydroxyflavones 18 Hexahydroxyflavones 19 Heptahydroxyflavones 20 Furanoflavones 21 VII. Survey of Natural Isoflavones 22 Polycyclic Compounds Containing the Isoflavone or Isoflavanone Nucleus 23 VIII. Absorption Spectra of Flavones and Isoflavones 25 Ultraviolet Spectra. 25 Infrared Spectra. 28 IX. Determination of the Structure of Flavones and Isoflavones 28 Degradation of Isoflavones 33 X. Synt4esis of Flavones 34 XI. Synthesis of Isoflavones 41 XII. Synthesis of Flavone and Isoflavone Glycosides. 44 XIII. Biogenesis of Flavo~es and Isoflavones. 45 XIV. Physiological Properties of Flavones and Isoflavones 48 Flavones 48 T"oflavones 50 ~ IV / Inhaltsverzeichnis. COnten~ -Table des matieres. xv. Tables 51 I. Visible Color and ;'max of Methanolic Solutions of some Flavones after Reduction with Mg and HCl 51 2. Trihydroxyf1avones and their Methyl Ethers 51 3. Tetrahydroxyf1avones and their Methyl Ethers. 52 4. Quercetin and its Derivatives : 53 5. Pentahydroxyf1avones other than Quercetin and their Methyl or Methylene Ethers. 54 6. Hexahydroxyf1avones and their Derivatives. 55 7. Natural Isof1avones 56 8. Ultraviolet Absorption Spectra of some. Naturally Occurring Flavones in Ethanol. 57 9. Ultraviolet Absorption Spectra of some Naturally Occurring Isof1avones in Ethanol 58 10. Hydroxyl and Carbonyl Frequencies of some Naturally Occurring Flavonoids 58 References 59 Fortschritte der Chemie der Vitamine D und ihrer Abkommlinge. Von H. H. INHOFFEN und K. IRMSCHER, Organisch-chemisches Institut der Technischen HoChschule Braunschweig 70 I. Konstitution der Vitamine D und ihrer Abkommlinge. 71 I. Vitamine D. 71 2. 5.6-t'.ans-VitamineD 72 3. iSO-Vitamine D. 75 4. Praecalciferole 76 5. Tachysterine 79 6. iso-Tachysterine 81 7. u- Tachysterin 82 8. Pyrotachysterin(e) 83 9; Suprasterine 83 10. Dihydro-Verbindungen 85 II. C(8)-Ketone 89 II. Neue Abbauprodl1kte der VitamineD 90 I. Die stereoisomeren 5,6-Dihydroxy-Vitarnine D8 90 2. Die t'.ans-C,D-Abbau-alkohole 90 3. Die Seitenketten-alkohole 91 4. Seitenketten-acetoxy-aldehyde , 92 5.. Das 8-Methyl-t'.ans-hydrindanol-(4)-on-(I) und die 8-Methyl- hydrindandione 92 III. Photochemische Isomerisierung 93 IV. Thermische Isomerisierung 96 V. Chemische Isomerisierung : 98 VI. Ergebnisse von BARON, L~ BOULCH und RAour. 99 VII. Verschiedene Verbindungen : 102 " I. Atio-Analoga der Praecalcifer01e und der Vitamine D. 102 2. VitaminD-hom010ge Verbindung , 103 3. Strukturisomere Vitamin D-Verbindung 103 4. 9.10-Seco-D-Homo-Steroid-Verbindung 104 5. VitaminDm ,., 105 VIII. Partialsynthesen 105 ,; I. 3-Desoxy-14P-praecalcifer012 105 2. iso-Vitamin D2-methylather-C(2)-Epimerengemisch und iso-Tachy- sterin-methylather-C(8)-Epimerengemisch 106 3. 3-Desoxy-iso-tachysterine 107 4. 6.7-cis-iso-Tachysterin2-methylather-C(8)-Epimerengemisch. 107 IX. Tota1synthese des VitaminsD8 108 I. Das Hydrindansystem 109 2, Die Seitenkette 110 3. Trienchromophor. Epimeren-trennung, trans- cis-Isomerisierung ..116 Literaturverzeichnis 118 Neuere Ergebnisse der Chemie pflanzlicher Bitterstoffe. Yon F. KORTE, H. BARKEMEYER und I. KORTE, Chemisches lnstitut der Universitat Bonn. 124 I. Einleitung 125 Der bittere Geschmack und die Bestimmung des Bitterwertes 126 Therapeutische Verwendung der Bitterstoffe. 127 W\rtschaftliche Bedeutung der Bitterstoffe. 128 II. Bitterstoffe der Gentianaceen 129 ciF I. Gentiopikrin. 130 ~ 2. Amarogentin 132 ;-. 3. Loganin. : , 133 III. Bitterstoffe der Asclepiadaceen 135 I. Kondurangin 135 2. Vincetoxin 137 IV. Bitterstoffe der Compositen 137 I. Absinthin und Anabsinthin 138 2. Cnicin 139 3. Lactucin und Lactucopikrin 140 4. Tenulin 144 5. Helenalin 147 6. Alantolactone : 149 V. Bitterstoffe der Menispermaceen 151 I. Columbin 151 2. Picrotoxinin (Picrotoxin) 155 VI. Bitterstoffe der Coriariaceen 161 Tutin und Coriamyrtin 161 VI Inhaltsverzeichnis. Contents. Table des matieres. VII. BitterstoffeHopfenbitterstoffe: der Urticaceen Humulon. Lupulon, Humulinon 162 162 LiteraturverzeichnisVIII. IX. X. TabellenMarrubiin.PlumieridBitterstoffe der LabiatenApocynaceen 165 165 168 168 173 17, Alkaloide aus Calebassencurare und siidamerikanischen Strychnosarten. vonK. BERNAUER, Ch~misches Institut der Universitat Zurich. I83 I. Einleitung I84 II. Die Entwick1ung der Chemie der Calebassen-Alkaloide I86 III. Die Auftrennung des Cal~bassencurare in Einzelalkaloide I87 IV. Die Alkaloide sudamerikanischer Strychnosarten I89 " " I. -obersicht I89 2. Die Alkaloide aus Strychnos toxifera :' I89 3. Die Alkaloide aus St1'. melinoniana BAILLON. I9O 4. Die Alkaloide aus Str. amazonica KRUK.. Str. macroPhylla und Str. guianensis (AUBL.) MART I9I 5. Diabolin und Desacetyl-diabolin aus Str. diaboU SANDW. I9I V. Die Elektronenspektren der Alkaloide aus Calebassencurare und sudamerikanischen Strychnosarten , I9I VI. Konstitution von Calebassen- und sudamerikanischen Strychnos- AlkaloidenA.B. Alkaloide2.3.4.5.6.Alkaloide7.I.2. 3.4. 5.6.I. VorbemerkungMelinonin-AMelinonin-B-obersichtLochnerinMelinonin.EMelinonin-GC-Mavacurin,-obersichtC-DihydrotoxiferinC-Toxiferin-IC-FluorocurarinC-Curarin-I.C-Calebassin vomvom und Yohimbin-TypusStrychnin-TypusundC-Alkaloid-Y Lochneram..., Caracurin-V und C-Fluorocurin :. 194~~v 194 195 195 195 200 202 202 204 204 205 205 207 211 215 218 ~~" 7. Experimentelle Verknupfung und Systematik der Alkaloide vom Strychnin- Typus 226 VII. Zur Biogenese der Alkaloide aus Calebassencurare und sudainerikanischen Strvchnosarten :...u~~~ Inhaltsverzeichnis. -ContentS. -Table des matieres. VII VIII. Zur Pharmakologie der Alkaloide aus Calebassencurare und sud- amerikanischen Strychnosarten 232 I. Allgemeines 232 2. Der Maustest ~' 233 3. Curare-Wirkung und Nebenwirkungen 233 4. Resorption, Verteilung und Ausscheidung von Calebassen- Alkaloiden. ..; 234 5. Nachweis der FixieruRg des C-Curarins-I an den motorischen ~! Endplatten 234 ;;~-; 6. Kenstitution und Curare-Wirksamkeit 234 IX. Tabellen 236 I. Alkaloide aus Calebassencurare 236 2. Strychnosarten, die Calebassen-Alkaloide fuhren. 237 3. Aus sudamerikanischen Strychnosarten isolierte Alkaloide 238 ~ 4. Cale.ba~sen- und S~rychnos-Alkaloi~e nach UV-Spektren geordnet 239 , 5. Naturl1che Alkalolde vom Strychmn-Typus 240 Literaturverzeichnis 24I / Occurrence and Metabolism of Simple Indoles in Plants. By BRUCE B. STOWE, The Biological Laboratories, Harvard University, Cambridge, Massachusetts. 248 Introduction. 249 I. Volatile Indoles 250 I. Indole. 250 2. Skatole (3-Methylindole) 254 " II. Tryptophan and its Derivatives 255 I. L-Tryptophan [2-AIffinG-3-~-indole)-propionic Acid] 255 2. L-Abrine (AInino-N-methyltryptophan) 259 3. L-Hypaphorine (Tryptophan Betaine) 260 4. Malonyl-tryptophan 26I III. Indole Bases and Some Related Compounds. 26I .~ I. Gramine.[3-(Dimethy~aminome:hyl)-indole] 26I 2. Tryptamme [3-(2-Ammoethyl)-mdole] 262 3. AInino-N-~ethyltrYi>tamine 263 4. Amino-N.N-dimethyltryptamine and its N-Oxide 264 5. 5-Hydroxytryptamine [3-(2-Aminoethyl)-5-indolol] 264 6. 5-Methoxy-aInino- N -methyl-tryptamine [3-(2-MethylaIninoethyl)-5- methoxyindole] 265 ." 7. Bufotenine [3-(2-Dime1;hylaIninoethyl)-5-indolol] and its N-Oxide ...266 8. 5-Hydroxy-3-indoleacetic Acid 266 lV. Potential Precursors of 3-Indoleacetic Acid. 267 . c I. 3-Indoleaceta1dehyde 267 c 2. 3-Indoleacetonitrile 268 3. 3-Indolepyruvic Acid 270 4. Ascorbigen 272 V. 3-Indoleacetic Acid 273 Table des matieres. VI. Products Formed from 3-Indoleacetic Acid. 277 I. 3-Indolealdehyde. 277 2. Ethyl 3-Indoleacetate 278 3. 3-Indoleacetamide. 278 4. 3-Indoleacetylaspartic Acid 279 VII. Some Other Indoles 280 I. 3-Indolecarboxylic Acid. 280 2. 3-Indoleglycolic Acid. 280 3. Indican ~8I References 282 j Some Biochemical Aspects of Disease in Plants. By A. E. DIMOND, The Connecticut Agricultural Experiment Station, New Haven, Connecticut 298 I. Introduction. 298 II. Abnormal Growth in Plant Disease 299 I. Ethylene Production and its Effects 299 2. Gibberellin 301 3. Crown Gall Induction. 3°4 III. Abnormal Metabolic Pathways in 308 References.IV. V. 3.AbnormalConclusion2.I. fusaricPecticLycomarasmin Enzymes.Water Acid. Economy 315 "TO / The Chemical Structure of the Normal Human Hemoglobins. By W. A. SCHROEDER, California Institute of Technology, Pasad6na, California. 322 I. Introduction. 323 II. Nomenclature 324 III. The Hemoglobin Molecule as a Whole 326 1. Iron Content 326 2. The Molecular Weight 327 .3. The Shape of the Molecule 329 IV. The Prosthetic Group 330 V. The Linkage Between Heme and Globin. 331 VI. The Normal Human Hemoglobins 333 1. The Change in the Type of Hemoglobin in the Indiv:idual Human as a Function of 4ge 334 2. Does an Embryonic Hemoglobin Actually Exist? 335 ~~ VII. The Purity of Hemoglobin in Hemoglobin Preparations. 340 I. Isolation. :. 340 2. Effect of the Isolation Procedure on the Purity of Hemoglobin Preparations. :- 340 3. Heterogeneity of Hemoglobin Preparations 341 4. Biological Significance of the Heterogeneity of Hemoglobin Preparations ' ,., 347 VIII. Chemical Investigations of Hemoglobin, ., , , ., , , , , , , 348 I. Amino Acid Composition 349 a) Adult Hemoglobin 349 b) FetaLHemoglobin 353 c) Comparison of the Amino Acid Composition of Adult and Fetal Hemoglobin. 354 2. Sulfhydryl Groups 355 3. N-Terminal Amino Acid Residues and Sequences 357 a) Adult Hemoglobin. 357 b) Fetal Hemoglobin. 359 4. C-Terminal Amino Acid Residues 359 5. Investigation of Internal Sequences. 360 ~ 6. The Insolub~e Residue from T~tic H~drolysates 365 " 7. The Separatlon of the Polypeptlde Chams of Hemoglobm 365 IX. Discussion and Conclusions 368 .~ I. The Hemoglobin Molecule as a Whole .' 368 2. The Polypeptide Chains Themselves. 370 3. Final Remarks 371 References. 371 I Paleobiochemistry and Organic Geochemistry. By PHILIP H. ABELSON, Geophysical Laboratory, Carnegie Institution of Washington, Washing- ton.D.C 379 Introduction. 379 Major Constituents of Livi~g Matter 381 Preservation of Organic Substances 386 Organic Complexes of High Molecular Weight. 387 The Stability of Organic Substances 389 Organic Substances in Soils and Rocks 391 Amino Acids in Soils 391 Peats and Coals. 392 Amino Acids in Sediments 392 Amino Acids in Shells and Calcareous Tests 393 Amino Acids in Bone. : ...394 Lipides 396 Carbohydrates. 398 Carbohydrates in Fossils 3Q8 Porphyrins 398 Precambrian Occurrences 399 The Perspective.; , 400 References. 400 J The Electron Gas Theory of the Color of Natural and"Artificial Dyes: ,," Applications and Extensions. By HANS KUHN. Physikalisch.Chemi- . sches Institut der Universita.t Marburg a. d. Lahn 404"" I. Quantum Mechanical Determination of the Position of the Absorption Bands of Simple Dyes with an Unbranched, a Ring-Shaped. or a Branched Electron Gas. 405 I. A Simple Model of VitaminB12 405 2. A Simple Electron Gas Ring Model of the Phthalocyanines a1ld Benzo- porphyrines. 407 3. A Simple Model of Dyes with a Bra1lched Electron Gas. 41 I rr. A Refined One-dimensional Model Considering Irregularities of Potential along the Chain (Wave Shape Potential Model) ~c.,c...tI8 ,"" I. Qualitative Discussion of Some Quantum Mechanical Aspects of '"~ Polyenes and Symmetrical Cyanines 418 2. A Quantitative Treatment of the Light Absorption of Polye1les 422 3. Treatment of the Light Absorption of Polyacetylenes 427 4. Wave Shape Potential Model of Cyanines, Aza-cyanines and Some OtherDye Classes 427 5. A Simple Treatment of Polyenes, Polyacetylenes, and Unsymmetrical Cyanines (Sine Curve Potential Model) 428 rrr. The Two-dimensional Electron Gas Model. 430 IV. Intensity and Structure of Absorption Bands. 434 I. Oscillator Strength of an Absorption Band. 434 2. Strncture of Absorption Bands 441 References. 445 Namenverzeichnis.Sachverzeichnis. IndexIndex of of Subjects. Names. Index Index des des Matieres. Auteurs. 452 470 ~ ~ Inhaltsverzeichnis. Contents. -Table des matieres. Die Actinomycine. Von H. BROCKMANN, Organisch-chemi~hes. Institut der Universitat GOttingen , I ~ II. I. 4.3.2. Einleitung GewinnungI. ActinomycingemischeNomenklaturNomenk1aturNomenklaturreinerActinomycinEigenschaftenVonActinomycingemischIdentifizierungTrennungDie ActinomycingemischeStreptQmyces-Arten und von bildendenativerderEigenschaften und Actinomycingemischen.friiher ActinomycineAminosauregehalt A.ctinomycine...Z Actinomycingemische...der beschriebener Strept"myces-Arten produzierte dirigiertenC, der X und Actinomycine ActinomycingemischeActinomycingemische' IBiosynthese reiner ~ Actin6mycine ; '. ..,, I3 2 i' 4 4 6 ,i 6 ~ ., 8 9 9 ", Physikalische Eigenschaften I3 ,~ Chemische Eigenschaften I4 Molekulargewicht I4 Aminosauregehalt. I5 III. Die Konstitution der Actinomycine I7 I. Die Konstitution des Chromophors ; I7 Despeptido-actinomycin ; I7 t Konstitution des Despeptido-actinomycins ; I8 Synthese des Despeptido-actinomycins 20 Farbige Abbauprodukte der Saurehydrolyse. 2I Actinocinin 24 Konstitution des Actinomycin-Chromophors. 26 Synthese des Actinomycin-Chromophors 28 Reaktionen des Actinomycin-Chromophors 29 2. Die Konstitution des Peptidteils 3I Actinomycin Cs 33 Actinomycin ~ (I1;X1. D) 38 Actinomycin C2 ,... ;39 Actinomycin Xz , 40 Actinomycin Xop 4I Actinomycin ~" ; 42 3. Struktur-Variationen des Peptidteils 42 IV. Derivate der Actinomycine; ; 46 I. Derivate. die durch Veranderung des Peptidteils entstehen 46 2. Derivate. die durch Veranderung des Chromophors entstehen. 47 Literaturverzeichnis : 48 Natiirlich vorkommende Nitroverbindungen. Von M. PAILER, II. Chemi sches Institut der Universitat W~en ; , EinleitungIII. II. I. p-NitropropionsaureChloramphenicol.3.2.4.Aristolochiasauren.2. I. HerstellungIsolierungBestimmungNeueret)berSynthesen altere Arbeiten und desArbeiten des Konstitutionsermi1;tlungChloramphenicolsChloramphenicolszur Isolierung. Reindarstellungau£ biologischem und Wege Konstitutions 56 56 ~R 66 3.4. ermittlungKonstitution derder Aristolochiasaure-I.Aristolochiasaure-II 0. .. 68 7° 74 5. Weiteres Vorkommen von Aristolochiasauren und Isolierung unc Literaturverzeichnis Charakterisierung von strukturell verwandten Natursto££en 77 78 Derives guanidiques biologiques. Par N GUYEN V AN THOAI et J. ROCHE CollegeIntroduction de France, Biochimie generale et comparee. Paris. ; , 83 84 I.. 3.4.Structure2.1. FormationBiogenese.Nomenclature.Structqre et formation.par voie chimique , , 84 84 85 87 QO a. Formation par amidination successive: cas de l'arginine 90- - b- Formation par transformation d.autres composes guanidiques 92. - c- Formation par transamidination 94. II. Proprietes2-3.4.5.1.6- BasiciteCyclisationDegradationFormationOxydationa.Stabilite Deguanidylation generales. et des hydrolyse.biochimique sels 99. -b. Desamidination totale 99. -c- Des 9() 9() 97 98 99 00 amidination partielle 100. III. Methodes1. Reactionsa. Reaction generales d'identifica1;ion au diacetyled'analyse etlOZ. et d~ de -b. dosage. preparation. Reaction ..'. .., a. l.iX-naphtol 102. - 10'l 102 c. Reaction au nitroi>russiate ferrique 102. -d- Reaction a. la nin hydrine 103- !; BibliographieIV. Conclusions2-Repartition Chromatographie des derivesguanidiques sur papier et sur colonne. Electrophorese. 103 105 107 107 Inhaltsverzeichnis.. -Contents. -'Table des matieres. v - j Naturally Derived isoThiocyanates (Mustard Oil~) and Their Parent ~ Glucosides. By ANDERS KJJER, Organic Chemical Laboratory, Royal Veterinary and Agricultural College, Copenhagen. ::..,. I22 ..', ., I. Introduction. I23 .1 II. Historical Development :.. I23 III. Parent Glucosides I24 I. General Properties I24 2. Distribution in PlantTissues I26 3. Detection, Isolation, Separation and Determination. I27 a. Paper Chromatography I27. -b. Isolation and Separation Methods I28. -c. Quantitative Determination I29. 4. Chemical Structure ; I29 a. Earlier Formulation I29. -b. Revised Structures I3I. - . c. Synthesis I34. 5. Individual Glucosides. I35 IV. Enzymic Hydrolysis. I36 I. Distribution of Myrosinase I36 " 2. Properties of Myrosinase I37 V. Naturally Derived isoThiocyanates I38 I. General Properties I38 2. Detection, Isolation, Separation and Determi1+ation .; I39 a. Chromatographic Methods 139". -b. Isolation 4°. -c. Separa- tion 40. -d. Quantitative Determination I4I. 3. Chemical Structure I4J a. Saturated Alkyl isoThiocyanates I4I. -b. Unsaturated Alkyl ,d isoThiocyanates I42. -c. w-Methylthioalkyl isoThiocyanates and .- Related Sulphoxides and Sulphones 44. -Stereochemistry 47. - d. Aromatic isoThiocyanates I48. -e. Hydroxy-substituted iso- Thiocyanates I5°. -f. isoThiocyanates of Doubtful Structur~ I53. t VII.VT.~. Biological R()t"ni{'"l Di"trihlltion Properties of of isoThiocyanates isoThiocyanate and Glucosides Their Parent Glucosides .155I.S4 VIlI. Tables. :. I57 I. Crystalline isQThiocyanate Glucosides. Known at the End of I959 I57 2. Crystalline isQThiocyanate Glucoside Tetraacetates, Known at the Eiid of I959. I58 3. isQThiocyanat~ Glucosides with Established Side-chains. Known at the End of I959 I59 8 4. Molecular Rotations of Sulphoxide isQThiocyanates of Natural Origin, Some Derivatives and Related C{)mpounds I6o 5. The Occurrence of isQThiocyanates or Their Parent Glucosid~s in Species of the Family Crucifefae I6I 6. The Occurrence of isQThiocya¥ates C?r Their Parent Glucosides in . Families other than Cruciferae : I67 References. I69 , - 11 Die Farbst()ffe im Gefieder .derVogel. VGn QrTo V()LKER, ZOologisches 1;nstitut der Justus Liebig-Hochschule, Gie6en. ,,! ! .. VII.Literaturyerzeichnis III.IV.VI. II. v. I. , EinleitungCarotinoid.e(Lipochrome)Riickblick.6.4.5.7.2.3.8.2.I.Fluoreszierende.Pyrrolfarbst.offeChemisch I.2. 3. DieI. AstaxanthinLuteinPhysiologisch~PicofulyinRhodoxant.hinRoteZeaxanthinBeiKanarienxanthophyllTuracinKoproporphyrinPyrrolfarbstoffe gelben anderenPapageien Carqtinoide ungeklarte(Xa;nthophyll) und bzw.Arten rotengelbe G~ndl~gen im unbekannterAstacinFederpigmente Federfarbstoffe,FederfarbstoffeStoffwechsel der StrukturCarotinoid-Ablagerung der der Vogel Papageien " 179 179 180 181 181 18z 183 186 189 194 199 199 z03 z03 zo3 211 Z13 215 216 Z18 / v Cis.frans Isomeric Carotenoid Pigments. By L. ZECHME.ISTER, California III. p. I. Institute IntroductionNolllenc!atureNulllberSollleI.Sollle RelativeSterically HistoricalProperties of and Technology,Stabilities. .Unhindered Types Relllar!1:sof cisof cis CarotenoidsPasadena, cis onCarotenoids. ForlllsStereoisolllerislll California. 238. Steric -Sterically Hindrance.of Polyenes. Hindered cis 223 224 226 229 2~2 23!5 2'!8 Forllls 239. -Polycis Forn1s 239. IV. 3.4.2.Cis-transI. 2. MeltingRotatoryRelativeS(jmeSpectral RemarksIsomerism Points. EffectAdsorption Power. ofon..,. and trans-the. Affiniti~s UV Spectra Spectracis Isomerization of all-trans Carotenoidsin the Visible Region . 239 239 241 244 244 24" . 3. SPectral Effect of trans -cis Isomerizationin the Near Ultraviolet 4. Region:A Theoretical the cis-Peak Interpretation of Spectral PhenomeIia, : EspeciaUy of 249 'i. theSDectra cis-Peak at Extremelv Effect Low TemDeratures 155 6~ Inhaltsverzeichnis. -Contents. --Table des matieres. VII v. Preparation of cis Carotenoids by Direct Rearrangementof the All-trans i Form; ~ , 264 I. Therm~l Methods of cis-trans Isomerization. ~'... 264 (a) Spontaneous Rearrangement in Solution at Room Temperature 264 (b) cis-trans Isomerization in Refluxed Solutions. 265 (c) cis-trans Isomerization by Melting Crystals...; 265 2. Photochemical cis-trans Isomerization ih the Absente of Cat:a;Iysts ..2'68 3. cis-trans Isomerization by Iodine Catalysis, in t.ig~t ~ 269 4. cis-trans Isomerization by Acid Catalysis. ; 273 5. cis-trans Isomerization by Contact with Active Surfaces. 273 6. cis-trans Isomerization via Boron Trifluoride Complexes. 274 . 7. Bio-stereoisomerization 274 VI. Preparation of cis Carotenoids by Total Synthesis. 274 "c'c"y Cc VII. Naturally Occurring cis and Polycis Carotenoids. 279 I. Mono- and Dicis Carotenoids 279 2. Polycis Carotenoids 280 Prolycopene 283. -Further Polycis Lycopenes 287. -Proneuro- , ~ -sporene (Protetrahydrolycopene, Neoneurosporene P) 288. -Pro- y-carotene 29I. VIII. Some General Remarks on Configurational Assignments. 29I I. Stereoisomeric Types ' 29I 2. Number and Location of cis Double Bonds. 293 3. Configuration and Infrared Spectrum. 294 IX. Configurational Assignments in Certain Stereoisomeric Sets. 295 ~ I. Stereoisomeric Sets with Two Hydroaromatic Terminal Groups. ..295 " p-Carotene Set 295. -Cryptoxanthin Set 300. ,- Zeaxanthin ~ Set 300. -Isozeaxanthin Set 30I. -Echinenone Set 30I.. -Can- I thaxanthin Set 30I. -p-Carotene Monoepoxide Set 3°3. -p-Caro. tene Diepoxide Set 3°3. -3,4-Dehydro-p-carotene and 3,4,3',4'- Bisdehydro-p-carotene Sets 305. -I6,I6'-Homo-p-carotene Set 305. - r3,I3'-Bis-desmet4yl-p.ca,rot~ne Set 305.. -retrQ:-pehydrocarotene Set 306. -(X-Carotene Set 306. -(X-Cryptoxanthin (Physoxanthin) Set 3°7. -Lutein Set 308. -Tr9llixanthin .Set 30/). -3,4- Dehydro-(X-carotene Set 308. :- Taraxanthin Set 308. 2. Stere9isomeric Sets with One Hydroaromatic and One Aliphatic Terminal Group. 399 y-Carotene Set 309. -Gazaniaxanthin Set 3IO. -Celaxanthin Set 3IO. -Capsanthin Set 3IO. -Torularh9din ~t 3II. 3. Stereoisomeric Sets with Two Aliphatic Terminal G~oups. 3Ir Lycopene Set 3II. -Neurosporene Set 3I4.- Phytofluene Set3I5.~ Rhodoviolascin (Sprill9xanthin) Set 316. -Capsorubin Set 3I6. -'- Fucoxanthin Set 3i7. 4. Stereoisomeric Sets with Two Arolriatic Terminal Gr9ups. 3I8 I ;," 1,18~Diphenyl-3;7,I2,I~-tetramethyl-9Ctadecanonaene Set 3.X8. - Remeratene and IsOrenleratene Sets 3I9. -I,3.7,12,t6,18-Hexaphenyl- octadecanonaene Set 3I9. -..Naphthyl-carotene" Set 320. - VIII Irihaltsverzeichnis. JContents.. Table des mat x. Lower-m01ecular W!Jight Carotenoid-carboxylic Acids: Bixin and Crocetin 320 Bixin Set 320. -Crocetin Set 327. XI. Cis-trans Isomerism and Provitamin A Effect 0( Carotenoids. 33 I References. 334 j The Gibberellins. By,P..W. BRIAN, JOHN FREDERICK GROVE and J. MACMILLAN, Imperial Chemical Industries, Ltd., Akers Research Laboratories, The Frythe, Welwyn, Hertfortshire, England. 35° I. Introduction 35I II. The Chemistry of the Gibberellins 352 I. General Remarks 352 2. Nomenclature 354 3. The Chemistry of Gibberellic Acid 355 A. Structure of Gibberene 356 B. Structure of Gibberic Acid 358 (a) Gibberic Acid 358. -(b) epiGibberic Acid 364. C. Structure alid Stereochemistry of alloGibberic. Acid. 365 (a) alloGibberic Acid 365.. -(b) Absolute Configuration 369. - (c). epialloGibberic Acid 372. - D. Structure and Stereochemistry of Gibberellic Acid. 374 (a) Gibberellic Acid 374. -(b) Epimerisation at Position 2 in Gibbanes 382. -(c) Rearrangement of Gibb-3-ene I- 4a Lactones 385. -(d) Absolute Configuration 386. -(e) Miscellaneous ReactionS of Ring A 388. 4. Biogenesis of the Gibberellins 389 III. Occurrence of Gibberellins in Higher Plants. 390 IV. Effects on Plant Growth and Development. 394 I. Stem Growth 394/ A. Day-neutral Annuals, etc. 395 B. Herbaceous Plants Sensitive to Vemalisation or Photoperiod. ...395 C. Photoperiod-controlled Growth of Woody Plants. 397 D. Cell-extension or Cell-multiplication? 398 E. Mode of Action Studies: Interactions with Auxins. 399 F. Mode of Action Studies: Int~ractions with Light. 402 G. Other Interactions 4°3 2. Leaf GroWth 4°4 3. Root Growth. 405 A. Root Extension 4°5 B. Root Initiation on Stem Cuttings 405 C. Development of Ro_°t-nodules on Legumin?us Plants. 405 4. Floweri~g. 466 A. Rosette Plants Requiring Vernalisation or Long-days 406 B. Caulescent Plants Induced to Flower by Vernalisation or Long-day Photoperiods. : 406 C. Short-dav Plants. 407 Discu! 407 5.7.6. 8. FertilisationA.B.EffectsA.B. Discussion.B. A.C.Seed PollenAccelerationParthenocarpyFruit-swellingBreakingTheI:iormonal Germination on R6le Growth Lower andof of Interactions Dormancyof the Fruit Plants Germination. Gibberellins Growth , as Plant Hormones ReferencesV. DetectionI.2. Bioassay.Chemical and and Estimation Physical Methods.of Gibberellins j Selected Subjects in Sedimentation Analysis, with .Some Applications to Biochemistry. By J. W. WILLIAMS, Department of Chemistry, IntroductionGlossary I. TheBasicI.z. 3. Chargeb)Thea)b)a)Velocity ofUniversity DiffusionConservationTheSedimentation.Theory. Terms. Theory EffectsFlow Equation of of Equations. SedimentationWisconsin,of forMass. Two-Component, The Madison, Analysis.Continuity Wisconsin. IncompressibleEquation. Systems and 4. TheIts Uses...: Differential Equation , of the Ultracentrifuge , and Its Solutions. II. The Two Sedimentation Components. Velocity, Experiment and the Determination of Molecularz.1.3. MolecularDefinitionMolecular Weight. WeightsWeightand Evaluation(Two-~omponent, Determinationfrom Sedimentation of the bySedimentationIdealized Combination and Systems.).Diffusion. Coefficient. of Sedimentation 453 456 Coefficient and Intrinsic Viscosity :... 462 III. H6terogeneity1. Boundary Spreading:and the Form Negligible of the Diffusion,Boundary ConstantGradient Curve.Sedimentation .t6o; z. CoefficientBoundary Spreading: Appreciable Diffusion, Constant Sedimentation 466 Coefficient x Inhaltsverzeichnis. -Contents. -Table des matieres. 3. Boundary Spreading: Sharpening Effects of Concentration Dependence of Sedimentation Coefficient 473 4. The Johnston-Ogston Effect 477 5. Protein-Protein Interactions 480 a) Monomer~Polymer Equilibria : 482 b) Bimolecular Associations 484 c) Interconversion of Isomers 488 , IV. Three-Component Systems 489 I. Solvati9n : 489 2. Sedimentation Equilibrium in a Density Gradient. 492 References. ; 4.Q" Structure and Immunological Specificity of Polysaccharides. By MICHAEL HEIDELBERGER, College of Physicians and Surgeons, Columbia University, New York, and Institute of Microbiology, Rutgers, the State University, New Brunswick, New Jersey. .,.,~+~,~;t!c#;~,~~, 503 ,"' I. Introduction. 503 II. Chemistry of Capsular Polysaccharides of Pneumococcus and O-Poly- saccharides of.Salmonella 506 III. Cross-reactions of AntipneumoCOCCal Sera. 509 IV. Cross-reactions in Anti-Salmonella Sera. 517 V. Cross-reactions in Anti-Mycoplasma mycoides Serum. 518 VI. Conclusion 518 VII.Tables 519 I. Specific Capsular Polysaccharides of Pneumococcus and Polysaccharideii ~ of Cross-reacting Microorganisms 519 2. Polysaccharides which Precipitate Antipneumococcal and Other Sera to Strongly Moderately 520 - 3. Cross-reactions of Polysaccharides of Microorganisms in Anti- pneumococcal and Other Antisera 523 4. Cross-reactions of Animal and Plant Polysaccharides in Anti- pneumococcal and Other Antisera 525 References. .; "2q Namenverzeichnis.Sachverzeichnis. IndexIndex of of Subjects. Names. Index Index des des Matieres Auteurs. 537 557 t Inhaltsverzeichnis. Contents. -Table des matieres. J Medium-ring Terpenes. By F. SORM, Institute of Organic Chemistry and i Biochemistry, Czechoslovak Academy of Science, Prague I I- Introduction. I II. Terpenes Containing a Nine-Membered Carbon Ring. 3 J I. Caryophyllene :- 3 2. The Betulenols 7 III. Terpenes Containing an Eleven-Membered Carbon Ring 8 Humulene and Zerumbone 8 IV. Terpenes Containing a Ten-Membered Carbon Ring II I. Germacrone II 2- Lactones 15 Pyrethrosin I5. -Arctiopicrin 17- -Costunolide 18. -Bal- chanolide 19. -Isobalchanolide 19. -Hydroxybalchanolide 19. - Acetylba:lchanolide 19. -Cnicin 2I. -Parthenolide 23. .-' Aristo- lactone 24. -Biogenetic Relationships 24. V. Some Spectral Anomalies in Medium-ring Terpenes 25 ~ References , 27 j Recent Advances in the Chemistry of Azulenes and Natural Hydro- azulenes. By TETSUO NOZOE and SHO ITo, Faculty .of Science, Department of Chemistry, Tohoku University, Sendai, Japan. 32 I. Introduction. 33 II. Azulenes 34 I. Synthetic Methods 34 a) Syntheses with Dehydrogenation 34 b) Syntheses without Dehydrogenation. 35 c) Syntheses Starting from Troponoids and Heptafulvenes 36 2. Physical Properties 40 3. Chemical Properties 41 a) Electrophilic Substitutions 41 b) Free Radical Reactions 44 c) Nucleophilic Substitutions 44 d) Arylideneazulenium Salts and Related Compounds. :. 45 e) Formyl- and Some Other Acylazulenes 46 f) Mannich Base. ; 48 g) Amino- and Hydroxyazulenes : 49 h) Ring Formation on the Azulene Nucleus. ,;0 .. III. Naturally Occurring Hydroazulenes 5z I. Non-lactonic Hydroazulenes 53 " a) Guaiol and Bulnesol 53 b) Aromadendrene and Alloaromadendrene. 53 c) Globulol. Ledol and Viridiflorol 55 d) Palustrol 56 e) (X-Gurjunene 57 f) Cyclocolorenone. 58 g) Zierone 58 h) Tricyclovetivene. Tricyclovetivenol and Bicyclovetivenol. 58 i)Hinesol , ' 59 j) Carotol and Daucol ..: : 60 2. Lactonic Hydroazulenes 61 a) Arlabsin. Absinthin and Anabsinthin 61 b) Matrictn and Matricarin 64 I c) Lactucin 65 ,~ d) Cynaropicrin 67 e) Helenalin. Isohelenalin, Neohelenalin. Tenulin. Balduilin, and Mexicanin C 67 f) Geigerin and Geigerinin 72 g) Ambrosin and Damsin 74 h) Parthenin. 75 i) DehydrocostuS Lactone 76 3. Stereochemistry of Hydroazulenes 76 4. Azulene Precursors of Some Other Types. 78 Addendum. 79 IV. Tables. , 80 I. AzuleneDerivatives (since 1958) 80 4 2. Azulenium Salts and Other Related Polymethine Dyes. 105 References. 107 j Chemistry of the Natural Pyrethrins. By L. CROMBIE, Department of Chemistry, King's College (University of London), London, and M. ELLIOTT, Department of Insecticides and Fungicides, Rothamsted Experimental Station, Harpenden, Herts. 120 I. Introduction. 120 II. Nomenclature. 126 III. Isolation of Natural Rethrins 128 IV. Structure and Chemistry of Chrysanthemic and Pyrethric Acids. 129 V. Synthesis of Chrysanthemic and pyrethric Acids. 133 VI. Structure and Chemistry of pyrethrolone and Cinerolone. 137 pyrethrolone 137. -Ciner.olone I40. VII. Synthesis of cis-pyrethrolone and cis-Cinerolone 141 VIII. Synthesis of pyrethrins and Cinerins 145 IX. Allethrin. 146 X. Biosynthesis of the pyrethrins and Cinerins 148 XI.. Synergists for Rethrins 148 XII. The Insecticidal Activity of Natural and Closely Related Synthetic Rethrins 15° References. 155 j Conformational Analysis of Steroids and Related Natural Products. By D. H. R. BARTON and G. A. MORRISON, DepartmeI)tofChemistry, Imperial College of Science and Technology (University of London), London 165 I. Introduction ; 0 166 II. Definition of Conformation 167 III. The Existence of Preferred Conformations. 167 I. Acyclic Compounds 167 . 2. Cyclohexane Derivatives 168 a) Boat and Chair Conformations 168 b) Axial and Equatorial Bonds !69 c) Auwers-Skita Rules 171 d) Exceptions to the Usual Stability Relationships. 17Z e) Six-memberedRings Containing Trigonal Carbon Atoms. 175 3. Decalin Derivatives 176 4. Perhydroanthracenes and Perhydrophenanthrenes 177 5. Steroids. 0 177 a) Relation between Configuration and Conformation. 178 b) Stability of Ring Junction in Hydrindanones Incorporated into Fused Ring Systems 179 6. Triterpenoids 18z , IV. Conformational Analysis of Reactions Controlled by Steric Hindrance and Steric Compression 183 I. Axial and Equatorial Substituents 184 a) Esterification of Alcohols and Carboxylic Acids, and Hydrolysis of Esters 184 b) Strengths of Acids and Amines 187 c) Chromatographic Behaviour of Alcohols. 188 d) Oxidation of Secondary Alcohols with Chromium Trioxide. 188 e) Solvolysis ; 188 r 2. Reactivity of Carbonyl Groups 189 a) Formation of Carbonyl Derivatives. 189 I b) Hydride Reduction of Carbonyl Groups. 189 ~ 3. Cis Addition to Double Bonds 191 V. Spectroscopic Correlations 193 I. Infrared Spectra 193 a) G-O Vibrations : 194 b) O-H Stretching Frequency ', 194 c) C-Halogen Absorption 194 d) G-D Stretching.Frequencies 194 e)C=O Stretching Frequencies: : 194 f) Intramolecular Hydrogen Bonding. 195 VI Inhaltsverzeichnis. -Contents. -Table des matieres. 2. Ultraviolet Spectra 195 3. Proton Magnetic Resonance Spectra. 196 4. Optical Rotatory Dispersion 197 VI. Effect of Conformation on Reactions with Stereochemically Demanding Transition States 199 I. Reactions Involving Four Coplanar Centres. ...; 199 a) Bimolecular Elimination 199 b) Diaxial Electrophilic Addition 201 c) Opening of Epoxide Rings 202 d) Formation of Epoxide Rings, and Neighbouring Group Participation 205 e) 1,2-Diaxial Rearrangements 206 f) Ring Contraction and Ring Expansion ~e~ctions 206 2.. Reactions Involving Coplanar Cyclic Transition States 208 3. Deamination Reactions 209 4. Bromination and Protonation of Enols. 209 VII. Preferred Boat Conformations 212 VIII. Conformational Driving Forces 216 IX. Conformational Transmission 217 I. Long Range Effects 217 2. Reflex Interactions 222 X. Carbanion Reduction Processes 223 References. 22" J Biogenetic-type Syntheses of Natural Products. By E. E. VAN TAMELEN, Department of Chemistry, The University of Wisconsin, Madison, Wisconsin 242 Introduction. 243 I. Alkaloids. 248 I. Pyrrolidine and Piperidine Groups 248 Hygrine, Cuscohygrine 248. ~ Isopelletierine 249. -Lobelanine, Arecaidine 249. -Nicotine, Anabasine 250. -Atropine, Tropine, Tropinone 25I. -Pseudo-pelletierine, Meteloidine 252. 2. Quinolizidine Group. 252 Lupinine 252. -Sparteine 253. -Cytisine, Anagyrine, Thermo- psine 254. 3.Anthranilic Acid Group 255 Amyl-quinolines 255. -Vasicine 256. -Arborine 256. -Acridone alkaloids 256. 4. Isoquinoline Group. 257 Laudanosine, Berberine, Papaverine, Glaucine 258. -Norsalsoline, Norlaudanosine, Benzyl-tetrahydroisoquinolines, Cryptopine, Cory- daline 259. , 5. Indole Group. ; 260 Yohimbine 260. -Eleagnine 26I. -Strychnine 26I. -Gramine 263. -Physostigmine 263. -Rutaecarpine 264. -Cryptolepine 264. - Cinchonamine, Cinchonine 264. -Quinamine 265. - Inhaltsverzeichnis. -Contents. -Table des matieres. VII . II. Terpenes 266 I. Syntheses Involving Polyene Cyclization ; 266 Geraniol, Geraniolenes, Ionones 266. -Limonene 266. -Farnesol derivatives, Farnesic acid 267. . 2. Conversions and Partial Synt~eses 269 Squalene 269. -Hopenone-I 27°. -Friedelin 271. -Glutinone 271. -Lupeol, Ger~anicol 271. 3. Miscellaneous 271 !X-Terpinene, Ascaridol 271. -Santonin, Verbenone 271. -Lupulone. Humulone 272. -Iridomyrmecin 272. III. Some Other Natural Products 273 I. Monosaccharides 273 Fructose, Sorbose, Xylose, Arabinose, Ribose 274. -N-Acetyl- i neuraminic acid 274. 2. Porphyrins 274 Etioporphyrin 275. -?orphobilinogen, Uroporphyrinogen 275. - Uroporphyrin-1II 275. -Chlorophyll 277. 3. Vitamins. ; 277 Ergosterol, Vitamin Ds 277. -Riboflavin. LuInichrome 277. - pyridoxin 278. 4. Amino Acids and Peptides 278 Serine, Threonine, p-Hydroxyleucine 279. -Thyroxine 279. -Peptide formation 279. -Role of histidine residues 280. -Thioesters and amino acids 280. . 5. Phenol Oxidation Products 281 Hydroxyindoles 282. -Bufotenin 282. -Serotonin 282. - Xanthommatin 282. -Actinomycin antibiotics 283. -Usnic acid 283. -Griseofulvin 283. -Hypericin 284. References. 280; Der Kohlenhydratstoffwechsel im Roggen und Weizen. Von H. H. SCHLUBACH, Physio1ogisch-Chemisches Institut der Universita.t Miinchen 291 I. Die loslichen Kohlenhydrate im Roggen und ihre Konstitution. 291 II. Die loslichen Kohlenhydrate im Weizen und ihre Konstitution. 301 III. Die Biogenese der Polyfructosane im Roggen und Weizen.. 307 Literaturverzeichnis 312 Les phosphatases des vegetaux superieurs: repartition et action. Par JEAN EMILE COURTOIS et ANDREA LINO, Laboratoire de Chimie. Biologique, Faculte de Pharmacie de Paris. 316 Introduction 317 Definition 317. -Historique 318. -Classification generale des phosphatases 319. ~ I. LesI. ClassificationBases phosphomonoesterases de la classificationdes principaux 320. groupes -Les dephosphomonoesterases.principaux types de phospho. 320 320 monoesterases 32I. 2. Repartition dans les organes vegetaux. 323 a. Graines 323 Variations d'act;ivite selon l'origine botanique 323. -Purification et champ d'action 324. -Phosphatase d' A.mandier 324. -Phospha- tase de Moutarde-Blanche 326. -Son de Ble 328. -Influence de la germination sur l'activite phosphatasique 329. 3. d.Phosphomonoesterasesb.a. c. RepartitionLesTuberculesRacines,Feuilles phytases fleurs 335. et -Purification fruits. a action specifique 337. -specificite caracteristique 338. 33° 332 333 334 335 4. Actionb.b.a. ActionLesOrthophosphatesGeneralites osylphosphatasesdes des effecteurs anions. 34R. -Arseniates 348. -Fluorures 348. - 344 346 346 348 Molybdates 349. -Autres formateurs de complexes 35I. Namenver2eichnis.IV.Sachverzeichnis.Bibliographie.III. II. R6leConclusionsLes 5.6. ATPasesActionReversibilitec. phosphodiesterasespyrophosphatases physiologiqueAction transferante etIndex des Index apyrasesd'action cations. of des of Subjects. des phosphatasesNames. phosphomonoesterases. IndexIndex desdes MatieresAuteurs. ~ 00 351 00 353 00 354 00 358 ..359 .0 360 0. 360 , 0 363 .363 374 389 ~ Inhaltsverzeichnis. Contents. -Table des matieres. j Nitrogen-containing Metabolites of Fungi. By J. H.BIRKINSHAW and C. E. STICKINGS, London School of Hygiene and Tropical Medicine, London- ; 1. I. Introduction. I II. Compounds Containing Acyclic Nitrogen. 2 I. Amines 2 2. Quaternary Ammonium Compounds 4 3: Nitro- and Nitroso-Compounds...; 6 4. Polyacetylenes COntaining Nltrogen 7 III. Oligopeptides 7 I.V. HeterocyclicNitrogen.Compounds 15 I. pyrrole Derivatives 15 2. Simple Indole Derivatives 15 3. Ergot Alkaloids : '17 4. pyridine Derivatives 21 5. Quinoline Derivatives. 22 6. Azanthracene Derivative 23 7. Phenoxazone Derivatives 23 8. Pyrazine Derivatives 24 9. Purine Derivatives 27 V. Heterocyclic Compounds Containing Sulphur as well as Nitrogen. 28 I. The Penicillins. 28 2. Other Metabolites COntaining Sulphur. 3° VI. Concluding Remarks 32 References. 33 J Forschungen am Lignin. Von K. FREUDENBERG, Chemisches Institut der Universitat Heidelberg 4I I. Einleitung 41 II. Ligninpraparate 42 I. Milled-Wood-Lignin nach BJORKMAN 42 2. Ligninpraparate anderer Herstellung 43 3. Berechnung der Ligninan8.1ysen :.. 44 .III. Die Abbausauren. 45 IV. Die destruktive Hydrierung des Lignins.. 48 V. Weitere Eigenschaften des Lignins 49 VI. Diep-Hydroxy-zimtalkohole 5° VII. Die HerstellunEt des Dehvdrierungspolymerisates (DHl") 5° ~ ~ ---,!-:i! VI Inhaltsverzeichnis. -"- ('.l\nt"nt_q --. fable des matieres. XIII.VIII. XII. IX.XI. X. BemerkungenDieZurVergleichZwischenprodukte WachstumsprinzipienBindungBiochemie des desnatiirlichen zuund Ligninsder den iiber LigninbildungEntwiirfenVersuche andesund die Ligninsdes Kohlenhydrate.kiinstlichenmit eines Isotopen KonstitutionsschemasLignins. des 53 55 61 63 66 Literaturverzeichni"XIV. ConiferenligninsLaubholzlignin. Humus ... 67 68 60 Die Ubichinone (Coenzyme Q). Von 0. SCHINDLER, Forschungsinstitut II. I. Dr.A.WanderA.-G.,2.EinleitungIsolierung I. IsolierungErste Beobachtungenund von Vorkommen Ubichinon Bern zum der Vorkommenaus Ubichinone verschiedenen von Ubichinon tierischen Geweben 73 74 75 75 sowiea) Nachweis Mikroorga~ismen und Isolierung von Substanz SA (Ubichinon) durch 7.1 b) MORTONIsolierungvon und MitarbeiterUbichinon (Coenzym Q bzw.Coenzym Q275) durch 7'; c) FOLKERSIsolierung und von MitarbeiterUbichinon (Coenzym Q bzw. Coenzym Q275) durch 7Q III. IV. Ermittlung3.4.5.2.Physikalisch-chemische3.I. PapierchromatographischesUV-AbsorptionsspektrenIR-AbsorptionsspektrenKernresonanzspektrenSchmelzpunkte.Isolierung GREEN, der und CRANE, ~onstitution Nachweis HATEFI, Eigenschaften von der Verhalten LESTER, UbichinonUbichinone der WIDMER Ubichinone als durch Coferment und chemischen Mitarbeiter. Abbau 80 82 84 84 84 85 87 88 89 I. Reduktive Methylierung und ansch1ieBender oxydativer Abbau ... 89 VI. V. 2.UmwandlungsprodukteSynthesenI. ReduktiveChroman- der und AcetylierungUbichinone Chromen-Derivate der undUbichinone anschlieBende von Ubichinon Ozonisierung (Substanz SC) ... 89 92 96 96 J.,iVIII. VII. IX. tera BedeutungBiochemische2.BiosynthesePlastochinon t1l Alkoxy-HomologeTVeTzei der" der h (KOFLERSBedeutung ni Lipide Ubichinone~ der fiir Chinon, derUb.ichinone Electron-Transport-Systeme Ubichinone. Coenzym Q254) TOT " Naturally Occurring Aromatic Derivatives of Monocyclic (X-pyrones. . By WALTER B. MORS, MAURO TAVEIRA MAGALHAES an:d OTTO RICHARD GOTTLIEB, Ministerio da Agricultura, Instituto,de Quimica Agricola. Riode Janeiro..., ~ 131 I. Introduction and Historical Development. 132 II. Structural Elucidation 133 I. (X-Pyrones not Methoxylated at C(4) 133 2. Partially Saturateq (at. 5.6) (X-Pyrones Methoxylated at C(4) 136 3. (X-pyrones Methoxylated at C(4) : 138 4. Characterization of (X- and 'Y-pyrones by Physical and Chemical Methods 141 5. The Mechanism of Alkaline Hydrolysis. 143 III. Syntheses 144 ~ I. Non-methoxylated (X-pyrones I44 a) Phenylcoumalin I44. -b) Paracotoin 144. 2. (X-Pyrones Methoxylated at C(4) I45 a) Yangonin 145. -b) II-Methoxy-yangonin and 5,6-Dehydro- met.hyst.icin 15°. -c) 5,6-Dehydrokawain 150. -d) 4-Methoxyphenyl- coumalin 15°. -e) Methoxyparacotoin 151. -f) Anibine 152. 3. Partially Saturated .(at 5,6) (X-Pyrones Methoxylated at C(4) 152 Kawain 152. -Methysticin 152. -Dihydromethysticin 152. - Dihydrokawain 152. IV. Physical Properties 154 V. PharmacologicalProperties : 154 VI. Taxonomic Significance of the Distribution of (X-pyrones in Lauraceae 158 VII. Reflections on Biosynthesis and Phylogenesis. 158 Addendum ; J6o References. 160 J Anthocvanins and their Sugar Components. By T. B. HARBORNE. John Innes Institute, Bayfordbury, Hertford, Herts, England. 165 I. Introduction. 165 II. Isolation. : 168 III. Properties of Anthocyanins 169 General Remarks 169 Spectral Characteristics 17° Chromatographic Properties 175 -I if Hydrolysis Products 176 Enzymic Degradation i77 IV. Identification of Anthocyanins 178 V. Natural Occurrence 179 Monosides. 179 , Biosides 182 Triosides : 183 Acylated Anthocyanins. 184 Anthocyanin-like Compounds 185 i VI. Distribution of Anthocyanins .. 186 .SystematicVII. TissueAnthocyaninsIntraspecific Variatiol;l. Relations.Variation. and ., Plant Colour 186 188 188 189 VIII. MetalCopigmentation.,Concentrati{)nBiosynthesisColour Complexesand Structure.of Anthocyanins .. 190 190 191 191 192 . IX.Conclusion , 194 References ;..., 195 Aminozucker, Synthesen und Vorkommen in Naturstoffen. Von GERHARD BASCHANG, Max-Planck-Institut rur medizinische Forschung. VerzeichnisII. I. Heidelberg.Einleitung.Allgemeine2.3.4.5.6.7.8.I. AcylierungHydrolyseEpimerisierungPerjodatoxydationDesaminierungMethylierung.Bestimmu:ngsmethodenGlykosidierung Aminozuckerder AbkiirzungenReaktionenundNomenklatur. der The Glykosidbindung 207. Rockefeller von -Sialinsiiuren Aminozuckern. Institute, 208. New York. : 200 202 202 204 204 204 205 206 206 2°7 2°7 2°7 III. I..Synthesen 2.3. Aminoaldosenm)Von b)I-Amino-2-keto-zuckei"d)a)h)k) g)c) n)e) 0) f) i) 1) CyanhydrinsyntheseHalbhydrierungEpoxydePhenylthiourethan-MethodeVerkiirzungEpisulfideNitroolefineHydrazinolyseEpimerisierungKonfigurat.ionsumkehrDialdehydeD-Glucosamin-Heyns-Carson-UmlagerungOxoglykosideN-Acetyl-neuraminsa.ure..Muraminsiiure Aminozuckern von Aminozuckernund und undder und undAmmoniak von(3-0-D-Lactyl-D-glucoSamin) Ammoniakundvonvon sichZuckerkette NitromethanPhenylhydrazin Ammoniak PhenylhydrazinSulfonsiiureesternD-Galaktosamin-uronsiiure2-Acetamino-zuckern Aminonitrilenableitende (Amine) Verbindungen. 208 208 208 208 209 210 210 211 211 212 212 212 213 2!4 214 215 215 217 217 218 218 F Inhaltsverzeichnis.. -Contents. -Table des matieres. IX IV. Aminozucker-haltige Naturstoffe 2I9 I. Mono-, Di- und Trisaccharide 2tt) a) Antibiotica ,: 2I9 b) Nucleotide. 220 2. HOhere Oligosaccharide. 22 I a) Oligosaccharide, aus Milch 22I b) Ganglioside. , 224 3. Polysaccharide. 226 a) Polysaccharide von Invertebraten und Pilzen. 227 Chitin 227. -Gala.ktosarnino&lykan 228. b) Bakterienpolysaccharide 228 Vi-Antigen 2z8 Neuraminsaure-haltige Polysaccharide. 228 I. Zellwandpolysaccharide228. -2. Somatische Polysaccharide 23°. -3. Ka.pselpolysaccharide 23I. c) Ul:onsaure- und schwefelsaure-haltige Polysaccharide (Mucop6ly- saccha.ride) 23I Hyaluronsii.ure 232. -Chondroitin-4-su1fat, Chondroitin-6-su1fat und Dermansu1fat 232. -Heparin 233. d) Glykoproteine 233 I. Submaxilla.ris-mucine 233. -2. Blutgruppensubstanzen (Fuco- mucine) 234. -3. Glykoproteine des Magens, aus Ascitesfliissig- keiten, aus Ham, aus Milch, aus Eik1ar 237 .-4. Plasmaproteine 240. -(Xl- und (X2-Glykoproteine 240. -Haptoglobine, Transferrine, Coeruloplasmine 24I. -Fetuin 242. -Thyreoglobulin 24Z. - y-Globuline z4z. -5. Hormone .und Fermente z43. -Gonado- tropine, thyreotropes Hormon 243. -Erythropoietin 243. -Kalli- krein, Enterokinase, Takaamylase A 243. V.. Enzymatischer Aufbau und Abbau von Aminozuckern. z44 I. Monosaccharide z44 a.) Glucosa.min und Galaktosamin 244 b) Mannosamin Z46 c) N-Acetyl-Ileuraminsaure z47 d) N-Acetyl-muraminsaure 247 2. Polysaccharide , Z48 a) Chitin. : 248 b) Uronsaure- und schwefelsaure-haltige Polysaccharide. Z48 c) Zellwand-polysaccharide 249 Literaturverzeichnis 250 J Structure and Stereochemistry of the Lycopodium Alkaloids. By KAREL WIESNER, Department of Chemistry, The University of New Brunswick, Fredericton, N.B.. Ca.nada Z7I 1. Introduction Z7I II. The Structure of Annotinine 272 The Relationship of Functional Groups. ,. ...z7z Derivation of the Complete Annotinine Structure. z75 The Configuration of the Remaining Asymmetric Centers and Some Rearrangements , z80 x Inhaltsverzeichnis. -Contents.- Ts\.bie des matieres. III. The Structure of Lycopodine; 283 IV. The Structures of Some Related Alkaloids. 286 Acrifoline , 286 Annofoline 287 Fawcettiine and Clavolonine 288 V. Stereochemistry and Interrelations of Alkaloids with the Lycopodine Skeleton ( 288 VI. The pytidone and Pyridine Alkaloids of Lycopodium. 290 Selagine 290 The Obscurines arld Lycodine 293 VII. The Biogenesis of the Lycopodium Alkaloids. 294 References. 2afi J Newer Developments in the Field of Veratrum Alkaloids. By C. R. NARAYANAN, NationC1l Chemical Laboratory, Poona. India. 298 I. Introduction 300 Classification 300. -Occurrence 300. -Extraction 3°I. Part A. The Jerveratrum Alkaloids 301 II. Rubijervine and Isorubijervine 30I I. Structure and Configuration 301 2. Some Abnormal Dehydrogenation Products. 302 III. Jervine and Veratramine 304 I. Dehydrogenation Products 304 2. Structure of J ervi~e. 305 3. Structure of Veratramine 306 4. Jervine. Further Transformations. 3°7 5. Veratramine. Further Transformations. 311 IV. On the Configuration of Jervine and Veratramine 31I V. Glycosides of the Alkamines 312 VI. Alkaloids of Unknown Structure 312 I. Veratrobasine 312 2. Geralbine. 3I3 3. Amianthine 313 VII. PharI!1acological Activity 313 .. Part B. The Ceveratrum Alkaloids. 313 VIII. Occurrence 313 IX. Cevine :..'... 315 I. Dehydrogenation,Products and Skeletal Structure. 315 2~ Oxidation Products 3I7 a) Decevinic Acid 317. -b) Hexane- and Heptane-tetracarboxylic Acids 319. 3. Alkaline Isomerization Products. , ~20 ~ ~ '---' tnhaltsverzeichnls. ~Oolltentg.- Table desmatieres. XI 4. Assignment of Structure 322 5. Configuration 324 a) Rings A and B 324. -b) COnfiguration at C12o) 325. - c) Configuration at C(12P C(14) and CI17). (Th~ Two IsoIf1eric Ortho- acetates) 325. -The Relative Strain on the Ring D-Ortho- acetate 327. -d) Configuration at C(13P C(18P C(20) and C(22). (The Labile CI18)-Ester) 328. -e) X-Ray Study of the Cevine Configuration 333. ~ 6. Cevine Betaine 333 t 7. Natural Esters of Veracevine 334 i X. Germine 335 . I. Introduction. Alkalolds of the Germine Family. 335 2. Skeletal Structureof Germine ; 335 3. Alkaline Isomerization 335 ~ 4. Other Reactions 337 5. Periodate Oxidation and Structure 337 6. Configuration. .., 342 ! 7. Natural Esters of Germine 346 XI. Zygadenine. , 346 ~, I. Structure and Configuration 346 2..Natural Esters of Zygadenine 347 " XII. Protoverine 348 & I. Structure. 348 2. Configuration , , 351 3. Natural Esters of Protoverine 353 "t .' XIII. Some General Remarks 353 j XIV. Alkaloids of UnknoWIl Structure 354 I. Neosabadine 354 2. Veragenine 354 3. Fritillaria Alkaloids. 355 a) Imperialine 355. -b) Peimine. Peiminine and others 355. - c) Raddeanine 355. XV. Pharmacological Activity of Veratrum Alkaloids. 355 XVI. Synthetic Esters and their Pharmacological Effects. 356 XVII. Biogenesis of Veratrum Alkaloids. 358 I References. 361 , J Equilibrium Sedimentation of Macromolecules and Viruses in a Density Gradient. By JEROME VINOGRAD and JOHN E. HEARST, California Institute of Technology, P~sadena. California. 372 I. Intrt;>duction. 373 1 i II. Experimental Procedures , 377 , I. Experiments in the Analytical Ultracentrifuge. 380 , 1 2- Experiments in the Preparative Ultracentrifuge. , 382 3. The Time to Attain Equilibrium. .0 , - 383 4- a) Recording Absorption of ResultsOptics ,-,._- 383 383 b) Schlieren Optics ,-,-- 384 III. Theoreticald)c) AutoradiogramsPreparative Considerations Experiments. and Evaluation of Results. .. 384 3B5 ." 386 2.I.3- TheExperimental DistributionBuoyant 'DeterminationMediumof the Macrospecies.of Various0 ., Density Gradients. ~393 a) Composition Density Gradient ,...393 b) Compression Density Gradient 394 c) Physical Density Gradient " , 394 d} The Buoyancy Density Gradient , 394 e) The Effective Density Gradient.." , 394 4. The Determination of Buoyant Density. , 395 5, The Determination of the Solvated and the Anhydrous Molecular Weight. 396 6, Effects of Macrospecies Concentration. 397 7. Density Heterogeneity , , , 397 8. An Alternative Method for Evaluating Molecular Weights. 398 IV- Applications to Some Physical and Biological Problems. 398 I- The Net Solvation of DNA ' " 398 2. Tr~nsfer Experiments with Stable Isotopes. , too a) ReplicationofDNAinE:.coli ,... 4o0 ~,c,,~ b) R eplcalonol ' t . f DNA In- H 1ger' h F orms , 4O2 "" C) Conservation of Ribosomal RNA during Bacterial Growth. 402 d) Transfer of Genetic Information to Ribosomes by Template RN A 403 3. The Guanine-Cytosine (G-C) Content of D.NA in Various Organisms. .4o4 ) M- b ' a lcro la. 1 DNA ...,. .., 4°4 b) DNA in HigherForms 4o6 4. Separation of DNA Duplex Molecules into Single Strands and their Recombination into Double Strands, The Formation of Heterozygote Moiecules 406 5, The Buoyant Behavior of Bovine Mercaptalbumin and other Proteins 409 6. The Buoyant"Behavior of Viruses 4I2 a) Plant Viruses. ~12 b) Animal Viruses , 4I2 c) Bacterial Viruses 4I3 7. Buoyant Density Titrations 4I4 8. Buoyant Behavior of Synthetic High Polymers in Organic Density Gradients 416 V. Tables 417 I. Density versus Refractive Index Relations for Various Aqueous Salt Solutions. : 4I7 nhaltsverzeichni Conten1 ble des matieres. XIII 2. Variation of po X: [0-9\ Sulfate with and Solution Cesium Density. Chloride Solutions. 3. Densities of Cesiun. References. Current Theories on the Origin of Life. By N. H. HOROWITZ, California In;titute of Technology, Pasaden~, and STANLEY L. MI.LLER, Scripps II. I. InstitutionIntroduction.The " Nature for of Oceanography,Living Organisms La Jolla. California. ~ 423 423 425 Wh t . L . f ,.. ReferencesIV.III. 5.,The4.Space6.3.5.4.2.2.The I. I. d.b.Thed.b.EnergyThea.Conc'usionsNatureSomec.The e.a. c. f. OriginOrganic9xygenThePorphyrinThermalRadioactivityand UltravioletElectricGeneralSynthesis Research aHeterocatalyticEvolution SynthesisFormationPrimitiveStructure Geological Other OriginlSof Sources of the Phosphates.CommentsDischargesle. Energy.Life Problems of and.theSynthesis Light.ofAtmosphere Geneticandof of RecordofPurines on on OpticalOrganicProteins the Replicationthe theFu.nction CosmicOrigin Connected EarthMaterial Primitive andEarth Activity Compounds Pyrimidines.of Rays of , of Life thewith Earth. DNA Genetic the : Origin Material. of Life. 425 440 445 445 447 448 448 449 450 45° 40;0 454 Namenverzeichnis. Index of Names. Index des Auteurs 460 Sachverzeichnis. Index of Subjects. Index des Matieres 480