Synthese von diastereo- und enantio-selektiv deuterierten β,ε-, β,β-, β,γ- und γ,γ-Carotinen

Synthesis of Diastereo- and Enantioselectively Deuterated β,ε-, β,β-, β,γ- and γ,γ-Carotenes We describe the synthesis of (1′R, 6′S)-[16′, 16′, 16′-²H₃]-β, εcarotene, (1R, 1′R)-[16, 16, 16, 16′, 16′, 16′-²H₆]-β, β-carotene, (1′R, 6′S)-[16′, 16′, 16′-²H₃]-γ, γ-carotene and (1R, 1′R, 6S, 6′S)-[16, 16, 16, 16′, 16′, 16′-²H₆]-γ, γ-carotene by a multistep degradation of (4R, 5S, 10S)-[18, 18, 18-²H₃]-didehydroabietane to optically active deuterated β-, ε- and γ-C₁₁-endgroups and subsequent building up according to schemes \documentclass{article}\pagestyle{empty}\begin{document}${\rm C}_{11} \to {\rm C}_{14}^{C_{\mathop {26}\limits_ \to }} \to {\rm C}_{40} $\end{document} and C₁₁ → C₁₄; C₁₄+C₁₂+C₁₄→C₄₀. NMR.- and chiroptical data allow the identification of the geminal methyl groups in all these compounds. The optical activity of all-(E)-[²H₆]-β,β-carotene, which is solely due to the isotopically different substituent not directly attached to the chiral centres, is demonstrated by a significant CD.-effect at low temperature. Therefore, if an enzymatic cyclization of [17, 17, 17, 17′, 17′, 17′-²H₆]lycopine can be achieved, the steric course of the cyclization step would be derivable from NMR.- and CD.-spectra with very small samples of the isolated cyclic carotenes. A general scheme for the possible course of the cyclization steps is presented.     

Mass spectrometry of pyrrolo [2, 3- b] pyrazines and pyrazino [2, 3- b]indole

The first mass spectra of pyrrolo [2, 3-b] pyrazine and some of its derivatives and of pyrazino [2, 3-b] indole are reported and compared with those of related compounds. Differences between the spectra of some aryl substituted derivatives are described and discussed.     

Formation and amination of dibenz[b,f,-1]azapen-talene dianion: Attempted synthesis of dibenz[b,f,-1]azapentalene

Dibenz[b, f,-1]azapentalene dianion (3) was allowed to react with N,N diethyl - O - mesitylenesulfonylhydroxylamine (4) in order to obtain N,N - diethyl - 5,10 - dihydroindeno[1,2 - b] - indol - 10 - amine (11). The available data indicated that electron transfer processes were involved in the formation of 11. Attempts to obtain dibenz[b, f,-1]azapentalene (1) and 11 by Hofman elimination or by the reaction of 11 with trifluoroacetic acid were unsuccessful.     

Evidence for homo-conjugation between two revolving 14pi-electron systems in 10b-methyl-10c-[2-(10b,10c-dimethyl-10b,10c-dihydropyrenyl)]-10b,10c-dihydropyrene

Ring contraction followed by an elimination reaction on anti-9-methyl-18-trans-2-(10b,10c-dimethyl-10b,10c-dihydropyrenyl)-2,11-dithia[3,3]metacyclophane gave the desired compound 10b-methyl-10c-[2-(10b,10c-dimethyl-10b,10c-dihydropyrenyl)]-10b,10c-dihydropyrene. 1H NMR spectroscopic analysis indicated a ring current effect over a considerable distance from the macro-molecular plane of each of the aromatic rings with the two pi systems freely rotating. Bathochromic shifts and peak broadening in its electronic spectrum clearly supports the presence of through-space pi-pi interactions between the two aromatic rings. This should serve as a good model to verify homo-conjugation effect in such a novel system where the two pi systems are freely revolving.     

Reactivity of η-, γ-, and α-Al2O3 for ZnAl2O4 Formation

The rate of ZnAl₂O₄ formation was measured for η-, γ-; and α- Al₂O₃ in order to distinguish the reactivity of them. The reactivity decreased as follows: η- > γ- > α-Al₂O₃. The reaction rate fitted to Jander's equation and the activation energies calculated were 33, 47 and 113 Kcal/mol for η-, γ- and α-Al₂O₃ systems, respectively. These differences are explained by an assumption that η- and γ-Al₂O₃ resulted in a ZnAl₂O₄ with imperfect spinel structure, but α-Al₂O₃ gave the perfect spinel structure. This assumption is based on the theoretical consideration of the activation energy needed for the diffusion-controlled reaction and date of lattice constant of each ZnAl₂O₄ obtained from three aluminas. The fact that η-Al₂O₃ shows very high reactivity compared with that of γ-Al₂O₃ was found to be explained on the basis of Jander's equation, a comparison of specific surface area and the defect structures of the aluminas.     

Electron transfer from dibenzo[b,f]-1-azapentalene dianion: Attempted synthesis of dibenzo[b,f]-1-azapentalene

When dibenzo[b,f]-1-azapentalene dianion (3) was allowed to react with either iron (III) chloride or ethylene bromide, a one-electron transfer from3 took place readily to give the radical anion11. Further electron transfer from11 did not occur presumably due to the antiaromatic character of dibenzo[b,f]-1-azapentalene (1) that would have resulted. The radical anion11 underwent further transformation by hydrogen abstraction from the solvent to give 5,10-dihydroindeno[1,2-b]indole (2) and by dimerization to themeso and (R,S) isomers of 5,5,10,10-tetrahydro-10,10-biindeno[1,2-b]indole (4 a and4 b) respectively.

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Elektronentransfer von Dibenzo[b,f]-1-azapentalen-Dianion: Ein Versuch zur Synthese von Dibenzo[b,f]-1-azapentalen

Zusammenfassung Die Reaktion von Dibenzo[b,f]-1-azapentalen-Dianion (3) mit Eisen (III) oder Ethylenbromid ergab einen Ein-Elektronentransfer zum Radikalanion11. Ein weiterer Elektronentransfer fand nicht statt, vermutlich wegen des antiaromatischen Charakters von Dibenzo[b,f]-1-azapentalen (1), das dabei entstehen müßte. Das Radikalanion11 ergab unter Wasserstoffentzug aus dem Lösungsmittel 5,10-Dihydroindeno[1,2-b]indol (2), das weiter zummeso- bzw. (R,S)-5,5,10,10-tetrahydro-10,10-biindeno[1,2-b]indol (4 a bzw.4 b) dimerisierte.

     

Basicities and structures of 2-(N-arylaminomethylene)-3(2H)-benzo[b]thiophenones,-benzo[b]furanones,and -benzo[b]selenophenones

The ionization constants of the conjugate acids of the reaction series 2-(N-arylaminomethylene)-3(2H)-benzo[b]thiophenones,-benzo[b]furanones, and -benzo[b]selenophenones were determined by potentiometric titration in anhydrous acetonitrile. The electronic and vibrational spectroscopic data showed that the protonation center in the molecules of these compounds is the carbonyl oxygen atom. It was established by correlation analysis that N-aryl substituents affect the protonation center primarily via an induction mechanism.Communication XVIII from the series Basicities and structures of azomethines and their structural analogs. See [1] for communication XVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. pp. 619–623, May, 1977.     

The Effect of α-, β- and γ-Cyclodextrin on Wheat Dough and Bread Properties

Cyclodextrins (CDs) are cyclic oligosaccharides that have found widespread application in numerous fields. CDs have revealed a number of various health benefits, making them potentially useful food supplements and nutraceuticals. In this study, the impact of α-, β-, and γ-CD at different concentrations (up to 8% of the flour weight) on the wheat dough and bread properties were investigated. The impact on dough properties was assessed by alveograph analysis, and it was found that especially β-CD affected the viscoelastic properties. This behavior correlates well with a direct interaction of the CDs with the proteins of the gluten network. The impact on bread volume and bread staling was also assessed. The bread volume was in general not significantly affected by the addition of up to 4% CD, except for 4% α-CD, which slightly increased the bread volume. Larger concentrations of CDs lead to decreasing bread volumes. Bread staling was investigated by texture analysis and low field nuclear magnetic resonance spectroscopy (LF-NMR) measurements, and no effect of the addition of CDs on the staling was observed. Up to 4% CD can, therefore, be added to wheat bread with only minor effects on the dough and bread properties.     

One-Bond 13C, 13C-Spin Coupling in η4-, η3- and η2-Olefin Transition Metal Complexes

One-bond ¹³C, ¹³C-spin-coupling constants have been measured, with natural isotope abundance, in η⁴-diene, η³-allyl and η²-ene transition-metal carbonyl complexes. Typical values of ¹J(C,C) are given for Fe-, Ru- and Os-complexes with the three types of olefinic ligands. The effects of substituents and the structural significance of the C,C-coupling constants are discussed.     

Condensed pyridine bases synthesis of some benzo[b]furo[2,3-c]-, benzo[b]- thieno[2,3-c]-, and benzo[b]selenopheno[2,3-c]-quinolines

Summary Condensation of benzo[b]furan-3(2H-one, benzo[b]thiophen-3(2H)-one and benzo[b]selenophen-3(2H)-one with dimedone gives 2-(3-heteryl)dimedones. Acylation of the latter leads to the corresponding tetracyclic pyrylium salts, from which condensed quinolines are obtained. Some condensed quinoline derivatives are obtained by reaction of 1-oxo-1,2,3,4-tetrahydroheterene[2,3-c]quinolines with sodium borohydride, hydrazine, and hydroxylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 321–326, March, 1994.     

Hydroxide-promoted redox reactions in water of α-Phenyl-4-nitro-benzenemethanol, α-(p-Nitrophenyl)-4-pyridinemethanol,and α-(p-Nitrophenyl)-4-Pyridinemethanol N-Oxide steric inhibition of resonance

α-Phenyl-4-nitrobenzenemethanol ( 3 ) reacted with 1 M sodium hydroxide to yield 4, 4′-dibenzoyl-azoybenzene ( 5 ) (51%), 4-hydroxy-4′-benzoylazobenzene ( 6 ) and benzoic acid (12% each), and smaller amounts of 4-aminobenzophenone and 4-nitrobenzophenone. Both α-phenyl-2-nitrobenzenemethanol ( 9 ) and 3, 5-dimethyl-4-nitrobenzenemethanol ( 10a ) did not react with 1 M sodium hydroxide, presumably due to steric hindrance. α-(p-Nitrophenyl)-4-pyridinemethanol ( 14 ) and its N-oxide 11 with 1 M sodium hydroxide yielded 4,4′-diaroylazoxybenzenes 15a and 12a , respectively, 4,4′-diaroylazobenzenes 15b and 12b , respectively, as well as 4-hydroxy-4′-aroylazobenzenes 16 and 13 , respectively. The relative reaction rates were 11 > 14 > 3 . Studies with 11 showed that the nitro group is involved in the redox reaction in preference to the N-oxide group.     

Selected β2-, β3- and β2,3-Amino Acid Heterocyclic Derivatives and Their Biological Perspective

Heterocyclic moieties, especially five and six-membered rings containing nitrogen, oxygen or sulfur atoms, are broadly distributed in nature. Among them, synthetic and natural alike are pharmacologically active compounds and have always been at the forefront of attention due to their pharmacological properties. Heterocycles can be divided into different groups based on the presence of characteristic structural motifs. The presence of β-amino acid and heterocyclic core in one compound is very interesting; additionally, it very often plays a vital role in their biological activity. Usually, such compounds are not considered to be chemicals containing a β-amino acid motif; however, considering them as this class of compounds may open new routes of their preparation and application as new drug precursors or even drugs. The possibility of their application as nonproteinogenic amino acid residues in peptide or peptide derivatives synthesis to prepare a new class of compounds is also promising. This review highlights the actual state of knowledge about β-amino acid moiety-containing heterocycles presenting antiviral, anti-inflammatory, antibacterial compounds, anaplastic lymphoma kinase (ALK) inhibitors, as well as agonist and antagonists of the receptors.     

Studies on the behaviour of α-, β- and γ-cyclodextrins and some derivatives under reversed-phase liquid Chromatographic conditions

The separation processes of α-, β- and γ-cyclodextrins and their various methyl derivatives have been investigated with Knauer polarimetric (Chiralyser) and refractive index (RI) detectors. RP18 and RP8 hydrocarbon packings and an NH₂ bonded phase were applied as stationary phases. Aqueous methanolic or ethanolic solutions were used as mobile phases. It has been found that the Chiralyser detector response is approximately linear at low concentrations of solutes and that its detection capabilities are about 40 times better than those of the RI detector. Differences in the order of elution of α-, β- and γ-cyclodextrins have been observed for various stationary phases as well as for various mobile phase compositions. The optimal conditions for analytical determinations of cyclodextrins and their derivatives have been discussed.