Blätteralkohol (XVI)Blätteralkohol (XVII)

2-Methyl-4, 6-cyclohexadienaldehyde and n-butyraldehyde were treated with sodium in p-xylene to yield the aromatized “leaf alcohol reaction” product, 2-methyl-benzylalcohol, in a better yield than that with the cyclohexadienaldehyde alone. n-Butyric acid isolated from the reaction mixture unequivocally showed the operation of the “crossed Cannizzaro disproportionation” in this reaction, aliphatic aldehyde serving as the hydride donor. 2-Propyl-5-ethyl-4, 6-cyclohexadienaldehyde was obtained by the NaOH/H₂O-EtOH Michael-Aldol condensation of leaf aldehyde, gave 2-propyl-5-ethyl-benzylalcohol along with caproic acid.

On the basis of “leaf alcohol-reaction” mechanism, it was obtained following benzyl-alkohols; 2-methyl-, 2-propyl-, 2-methyl-5-ethyl-, 2-propyl-5-ethyl-benzylalcohol, from leaf alcohol and crotylalcohol.     

Blätteralkohol (X)

Durch Erhitzen von 3-cis-Hexen-l-ol (Blätteralkohol) mit Natrium wurde die aromatische Verbindung (2-Propyl-5-äthyl-benzylalkohol) hergestellt und auch aus 3-trans-, 2-cis-oder 2-trans-Hexen-l-ol, oder aus 2-trans-Hexen-l-al (Blätteraldehyd) wurde die gleiche Verbindung erhalten. Durch eine gleiche Reaktion, wurde aus 3-Penten-l-ol die aromatische Verbindung (2-Äthyl-5-methyl-benzylalkohol) und aus 2-trans -Buten-l-ol wurde 2-Methyl-benzylalkohol erhalten.

Wir möchten besonders diese interessante Reaktion, bei der aus αβ- oder βγ-ungesättigten, n-primären Alkoholen oder Aldehyden Benzylalkohole mit verschiedenen Substitutionen hergestellt werden, als “Blätteralkohol-Reaktion” bezeichnen.     

Blätteralkohol (IX)

Blätteraldehyd wurde durch die einfachste, ergiebigste Synthese dargestel1t. Demnach wurde es aufgeklärt, daß die Konfiguration des natürlichen Blätteraldehyds trans-Form ist.     

Blätteralkohol (VIII)

Es wurde aufgeklärt, daβ die im Tee-blättern weit verbreitet vorkommende natürliche Blätter-alcohol-fraction aus einern Gemisch der cis, trans-Isomere besteht, wobei bisher das cis-Isomere besteht, wobei bisher das cis-Isomere stark überwiegt.     

Synthese von O-(3-desoxy-α-d-manno-2-octulopyranosylonsäure)-(2→4)-O-(3-desoxy-α-d-manno-2-octulopyranosylonsäure)- (2→6)-O-(2-amino-2-desoxy-β-d-glucopyranosyl)-(1→6)-2-amino-2-desoxy-d-glucopyranose

Benzyl-3-O-benzyl-2-benzyloxycarbonylamino-6-O-[2-benzyloxycarbonyl-amino-2-deoxy-3,4-O-(tetraisopropyldisiloxane-1,3-diyl)- β-d-glucopyranosyl]-2-deoxy-α-d-glucopyranoside was coupled with methyl (4,5,7,8-tetra-O-acetyl-3-deoxy-α-d-manno-2-octulopyranosyl bromide)onate (13) to yield the α-glycosidically linked trisaccharide. After deacetylation and selective introduction of a second 7′,8′-O-tetraisopropyldisiloxane group, a further glycosidation reaction with 13 led regioselectively to the tetrasaccharide benzyl O-[methyl (4,5,7,8-tetra-O-acetyl-3-deoxy-α-d-manno-2-octulopyranosyl)onate]-(2→4)-O-{methyl [3-deoxy-7,8-O-(tetraisopropyldisiloxane-1,3-diyl)-α-d-manno-2-octulopyranosyl]-onate}-(2→6)-O- [2-benzyloxycarbonylamino-2-deoxy-3,4-O-(tetraisopropyldisiloxane-1,3-diyl)-β-d-glucopyranosyl]- (1→6)-3-O-benzyl-2-benzyloxycarbonyl-amino-2-deoxy-α-d-glucopyranoside. A series of deblocking steps gave O-(3-deoxy-α-d-manno-2-octulopyranosylonic acid)-(2→4)-O-(3-deoxy-α-d-manno-2-octulopyranosylonic acid)- (2→6)-O-(2-amino-2-deoxy-β-d-glucopyranosyl)-(1→6)-2-amino-2-deoxy-d-glucopyranose which was identical with a tetrasaccharide that had been isolated by hydrazinolysis of the lipopolysaccharide from Salmonella minnesota R 595. Hence, synthetic proof is provided for the linkages in this part of the inner core region of lipopolysaccharides.     

Zur frage des Stärkeabbaues beim Welken der Blätter

Ohne Zusammenfassung     

CO2-Gaswechsel amphistomatischer Blätter

Summary The leaves of Primula palinuri and Zea mays are amphistomatic. The CO₂-exchange of both leaf surfaces was measured separately. The distribution of stomata and the portion of CO₂-uptake of both leaf surfaces correspond well. In Primula the greater part diffuses through the upper surface of the leaf, in Zea through the lower surface. Stripping of the Primula epidermis does not change the total CO₂-uptake but the greater part now diffuses through the lower stripped surface of the leaf. The CO₂-uptake of the upper surface alone, as well as of the lower surface alone and of both surfaces together was measured. The quantities of CO₂ transported through the leaf surfaces are not independent of each other: if CO₂-uptake is only possible through one surface of the leaf the CO₂ flux on this side increases. The significance of this property of amphistomatic leaves in relation to transpiration and CO₂ assimilation is discussed.     

CO2-Gaswechsel amphistomatischer Blätter

Summary The time-response of the CO₂-exchange of both leaf surfaces was measured separately. Leaves of Primula palinuri and Zea mays were used for the study. After short dark-periods (3 min) the stomata are not closed. Consequently CO₂-uptake starts quickly after re-illumination and reaches the steady-state value very rapidly. The time-response of stripped leaves of Primula and of normal leaves after short dark-periods is identical. Accordingly, the conclusion seems to be evident that in both cases we are measuring the time-response of photosynthesis, which is not influenced by stomatal reactions. After long dark-periods (60 min) the stomata are closed. After re-illumination the CO₂ released by respiration is immediately reassimilated. There is a distinct lag-phase in time-response which is more or less located in the CO₂-compensation point. This lag-phase is of different length for both leaf surfaces, and is interpreted as being the lag-phase of stomatal opening reactions. The consequence of the observed different time response of photosynthesis and stomatal reactions is discussed: under non-steady-state conditions photosynthesis is limited by slow stomatal opening reactions.     

Synthese von 1,3,5-Triazinen aus Aminosäure-Derivaten (III)

An extracellular acidic polysaccharide produced by Serratia piscatorum IFO 12527 was found to exhibit a marked antiinflammatory activity. The polysaccharide was purified by fractional precipitation with cetyltrimethylammonium bromide and then by gel filtration on Sepharose 2B to give two homogeneous fractions, PLS N–I and PLS N–II, the former exhibiting the antiinflammatory activity.

PLS N-I was a complex polysaccharide composed of l-rhamnose, d-galactose and d-galacturonic acid in the molar ratio of 2: 1; 1, together with small portions of d-glucosamine, d-galactosamine, protein and fatty acids such as acetic, lauric, myristic, β-hydroxyrnyristic and palmitic acids. Physicochemical and biological properties of PLS N–I and PLS N–II were also described.     

Kleinere Arbeiten des pflanzenphysiologischen Institutes der Wiener Universität XIV

Ohne Zusammenfassung     

Beiträge zur Blütenbiologie des Sanddorns (Hippophae rhamnoides L.)

Ohne ZusammenfassungMit 10 Textabbildungen.Herrn Prof. Dr.E. Leick, Hiddensee, zum 70. Geburtstage gewidmet.     

The Synthesis and Antiviral Activity of (E)-5-(2-Nitrovinyl)uridine and (E)-5-(2-Nitrovinyl)-2′-deoxyuridine

Abstract

The protection of the sugar moiety of a 5-formyluracil nucleoside with acid-labile protecting groups allows for the deprotection of the sugar of a subsequently formed nucleoside possessing a 5-nitrovinyl side-chain. The synthesis and antiviral activity of (E) -5-(2-nitrovinyl)-uridine and (E)-5-(2-nitrovinyl)-2′-deoxyuridine are reported.     

Synthese und Abbau der Nucleinsäuren während der Entwicklung des Makronukleus von Stylonychia mytilus (Protozoa,Ciliata)

Zusammenfassung Es wurde die Nukleinsäuresynthese während der Entwicklung der Makronukleusanlage vom diploiden Kern zum polyploiden Makronukleus untersucht. Die Nucleinsäuren wurden mit ³H-Thymidin und ³H-Uridin markiert. Dabei ergab sich:1.Während einer ersten Polyploidisierungsphase baut die Anlage ³H-Thymidin in ihre DNS ein. Am Ende dieser Phase ist die nunmehr polyploide Anlage stark markiert. Einige Stunden später jedoch, während der DNS-armen Phase, ist der größte Teil der Markierung verschwunden (Autoradiographien). Daraus wird gefolgert, daß die meiste DNS aus der Anlage verschwindet. Scintillationsspektrometrische Messungen zeigten, daß die DNS-Menge der Exkonjuganten um mehr als 90% reduziert wird. Diese Ergebnisse stimmen mit spektrophotometrischen Befunden (Ammermann, 1965) überein. 2. Auf das DNS-arme Stadium folgt eine zweite Polyploidisierungsphase, in welcher der endgültige polyploide Makronukleus heranwächst. Dabei wird neu aufgenommenes Thymidin eingebaut. 3. Weder in der Anlage mit Riesenchromosomen (am Ende der ersten Polyploidisierungsphase) noch in der DNS-armen Anlage noch in den Fragmenten des alten Makronukleus konnte eine RNS-Synthese nachgewiesen werden. Sie setzt erst mit dem Beginn der zweiten Polyploidisierungsphase ein (Autoradiographien).

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Synthesis and decomposition of nucleic acids during macronuclear development in Stylonychia mytilus

The synthesis of nucleic acids during the development of the macronuclear anlage from a diploid nucleus to the polyploid macronucleus has been studied. The nucleic acids were labeled with ³H-thymidine and ³H-uridine. The following results have been obtained: 1. In the first polyploidization stage the anlage incorporates ³H-thymidine into its DNA. At the end of this stage the anlage is polyploid and strongly labeled. Some hours later, during the DNA-poor stage, most of the labeling has disappeared (autoradiographs). This indicates that most of the anlagen-DNA is decomposed. Scintillation counter measurements showed that only about 9 per cent of the DNA stays within the exconjugants. These data agree with earlier spectrophotometric results (Ammermann, 1965). 2. The DNA-poor stage is followed by a second polyploidization stage in which the definitive polyploid macronucleus develops. Completely new thymidine is incorporated during this stage. 3. RNA synthesis does not occur neither in the giant chromosome anlage (end of the first polyploidization stage), nor in the DNA-poor stage, nor in the fragments of the old macronucleus. RNA synthesis starts at the beginning of the second polyploidization stage (autoradiographs).

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Mit Unterstützung durch die Deutsche Forschungsgemeinschaft.     

Microbiological synthesis of 5-ethyl- and (E)-5-(2-bromovinyl)-2′-deoxyuridine

Summary The title compounds were prepared by an enzymatic transdeoxyribosylation from 2 dGuo or 2 dThd to the respective heterocyclic bases, 5-ethyluracil and (E)-5-(2-bromovinyl)uracil, using the whole bacterial cells ofEscherichia coli as a biocatalyst.     

Synthese der amadori-verbindung: 2-desoxy-2-[(1-desoxy-D-fructofuranuronsäure)-1-yl]amino-α-D-glucopyranose

Condensation of 2-amino-2-deoxy-D-glucose hydrochloride with D-glucuronic acid in methanol containing a trace of pyridine gave crystalline 2-deoxy-2-[(1-deoxy-D-fructofuranuronic acid)-1-yl]amino-α-D-glucopyranose (2) in a yield of 34%. The compound was characterized by analytical and spectroscopic data and by its hepta-O-acetyl derivative. At pH 6.5, 2 was split quantitatively into 2-amino-2-deoxy-D-glucose and D-glucuronic acid.