Harnessing anionic rearrangements on the benzenoid ring of quinoline for the synthesis of 6,6'-disubstituted 7,7'-dihydroxy-8,8'-biquinolyls

7,7'-Bis(((dimethylamino)carbonyl)oxy)-8,8'-biquinolyl (5) was prepared in 71% yield by regioselective directed ortho metalation (DoM) of N,N-dimethyl O-quinol-7-yl carbamate (2) with LDA followed by oxidation with anhydrous ferric chloride. DoM of 5 with excess LDA induced double anionic ortho-Fries rearrangement and gave 6,6'-bis((dimethylamino)carbonyl)-7,7'-dihydroxy-8,8'-biquinolyl (8). Treatment of N,N-diethyl O-(8-iodoquinol-7-yl) carbamate (16) with LDA in THF solvent at -78 degrees C, followed by addition of anhydrous ferric chloride, resulted in an efficient tandem halogen-dance dimerization process which afforded 7,7'-bis(((diethylamino)carbonyl)oxy)-6,6'-diiodo-8,8'-biquinolyl (17) directly in 54% yield.     

Protonic conduction in NH4H2PO4

The conductivity of ammonium dihydrogen phosphate has been measured as a function of temperature and dopant concentration. A previously disputed break in the log conductivity vs reciprocal temperature plots has been observed. The activation energy is in agreement with previous work on NH₄H₂PO₄. In addition, the conductivity vs concentration of NH₄HSO₄ plot is linear, permitting the calculation of the L defect mobility and indicating that the proton is the conducting species. It is concluded that the mechanism of conduction is the same as previously proposed for KH₂PO₄ and KH₂AsO₄.     

Interactions magnétiques dans des groupements binucléaires du Ruthénium +V

The cationic ordering in the $\text{Ba}\text{M}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Ru}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{O}{}_3\text{(M =}\text{Mg, Ca, Cd, Sr}\text{)}$ oxides which crystallize with the 6H structure gives rise to Ru⁵⁺Ru⁵⁺ pairs in (Ru₂O₉) clusters. The magnetic properties have been analyzed on the basis of the Heisenberg-Dirac-Van Vleck model: The d electrons are localized on each Ru⁵⁺ ion and interact strongly through antiferromagnetic exchange. The susceptibility curves agree with the H.D.V.V. model. The values of the exchange integrals have been determined by fitting the experimental values.     

5α-24-Norcholestan-3β-ol and (24Z)-Stigmasta-5,7,24(28)-trien-3β-ol,Two New Marine Sterols from the Pacific Sponges Terpios zeteki and Dysidea herbacea

The steroidal components of 2 marine sponges, Terpios zeteki (from Hawaii) and Dysidea herbacea (from Australia) were fractionated through a combination of chromatographic methods, including reversed phase HPLC., and were analyzed by a combination of physical methods, including high resolution GC.-MS. and 360 MHz ¹H-NMR. T. zeteki contains 6 conventional 5α-stanols which comprise 91% of the sterol mixture, and traces (0.5%) of a new C₂₆ sterol, 5α-24-norcholestan-3β-ol. Minor amounts of conventional Δ⁵-sterols (6.5%) and of a single Δ⁴-3-ketosteroid (1.5%) were also present. In contrast, the Australian sponge (D. herbacea) contains 3 Δ^5,7-sterols which comprise 1.5% of the sterol mixture, and one new C₂₉ sterol, (24 Z)-stigmasta-5,7,24(28)-trien-3β-ol, as the major component (75%). In addition, minor amounts of conventional 5α-stanols (0.5%), Δ⁵-sterols (5%) and 5α-Δ⁷-sterols (18%) were present in this complex sterol mixture. The possible dietary or endosymbiotic origins of these sterols are discussed.     

EMF-measurements with galvanic bromine cells in the systems RBr/MBr2 (M=Sr,Ba)

The systems RbBr/SrBr₂ and RbBr/BaBr₂ were reinvestigated by DTA and X-ray-crystallography. Additionally to the known compounds RbSrBr₃, RbSr₂Br₅ and RbBa₂Br₅, the phases Rb_2.23Sr_0.885Br₄ and Rb_2.13 Ba_0.935Br₄ were found, which are structural related to the Th₃ P₄ — type. By EMF-measurements the thermodynamic functions G, H and S were determined for all compounds.

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Zusammenfassung Die Systeme RbBr/SrBr₂ und RbBr/BaBr₂ wurden mittels DTA und Röntgenaufnahmen an Kristallpulvern neu untersucht. Zusätzlich zu den schon bekannten Verbindungen RbSrBr₃, RbSr₂Br₅ und RbBa₂Br₅ wurden die Phasen Rb_2,23Sr_0,885Br₄ und Rb_2,13Ba_0,935Br₄, die sich strukturell vom Th₃P₄-Typ ableiten lassen, neu gefunden. Für alle Verbindungen wurden durch EMK-Messungen in galvanischen Feststoffzellen die thermodynamischen Funktionen G, H und S bestimmt.

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RbBr/SrBr RbBBr/BaBr₂. RbSrBr₃, Rbsr₂Br₅ RbBa₂Br₅, Rb_2,23Sr_0,885Br₄ Rb_2,I3Ba_0,935Br₄, Th₃P₄. $ G, H S.

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This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.     

The synthesis of annulated pyridazines by cycloaddition of azodicarboxylates to vinyl heterocycles

Reaction between 2-vinyl pyridine and azodicarboxylates 2 or 5 gives N,N'-disubstituted tetrahydropyrido[3,2-c]pyridazines 3 and 6, and dihydro-3H-pyrido[1,2-c]triazines 4 and 7; 2-(prop-1-en-1-yl)-pyridine 8 gives hydropyridopyridazines 10 and 11 but 2-(prop-1-en-2-yl)pyridine 9 gives mainly the ‘ene’ addition product 12. From 4-vinyl-pyridine and esters 2 or 5 diesters of tetrahydropyrido[3,4-c]pyridazine-1,2-dicarboxylic acid, 25 and 26 are obtained, and from 2-methyl-5-vinylpyridine both possible cyclisation products, the tetrahydro-pyrido[2,3-c]pyridazines 33 and 36, and -pyrido[4,3-c]pyridazines 34 and 37. The di-t-butyl esters 6, 11, 26, and 37 are quantitatively decarbalkoxylated in TFA, giving tetrahydropyridopyridazines 16, 18, 27, and 41; of these, the first three were oxidized to give pyrido[2,3-c]-pyridazine 15, its 3-methyl derivative 19, and pyrido[3,4-c]pyridazine 28 respectively. A dihydropyrido[4,3-c]-pyridazine 42 was obtained from compound 41. Thieno[2,3-c]-pyridazine 48 has been similarly prepared from 2-vinylthiophen, but 2-(prop-1-en-2-yl)thiophen gave an ene addition compound 51 and a dihydrothienopyridazine 50. Reactions with other vinylpyridines, and with vinylfurans, were unsuccessful.     

Photoisomerization of 2H,6H-Thiin-3-ones to 2-(Alk-1-enyl)thietan-3-ones

Reaction of 3-bromo-3-methylbutan-2-one ( 1 ) with mercapto-esters 2 affords 5-oxo-3-thiahexanoates 3 which cyclize to thiane-3,5-diones 4 . Conversion of these dicarbonyl compounds to their ethyl enol ethers 5–7 followed by reduction with LiAlH₄ gives 2H,6H-thiin-3-ones 8–10 . On irradiation (350 nm) in either MeCN, benzene, or i-PrOH, these newly synthesized heterocycles isomerize efficiently to 2-(alk-l-enyl)thietan-3-ones 11–13 . The rearrangement seems to proceed from an excited singlet state, as it is not quenched by naphthalene, and also occurs with the same efficiency in the presence of added alkene. A (9-S-3) sulfuranyl-alkyl biradical formed by bonding of C(α) of the enone C?C bond on sulfur is discussed as possible intermediate.     

60Co-initiated copolymerization of styrene with vinyl acetate

The kinetic behavior of the ⁶⁰Co-initiated copolymerization at 25°C of styrene with vinyl acetate at 1100 and 2000 rad/hr was studied. As in the case of thermal and photochemical copolymerizations of these monomers, the growing chains are particularly rich in styrene units, and the overall rate is affected by a diluent effect due to the vinyl acetate monomer. However, in the case of the radiation copolymerization, this effect is partially counterbalanced by an increase of the initiation rate with the vinyl acetate concentration; the polymerization rate curve shows a maximum at a vinyl acetate molar fraction of 0.25. This effect is due to the very different free radical yields of these two monomers. The experimental results may be understood on the basis of a kinetic scheme which involves an energy transfer process from the excited vinyl acetate molecules to the styrene monomer and a termination reaction of the growing chains by very short styrene radicals when the mixture is rich in vinyl acetate.     

The effects of different dietary fiber pectin structures on the gastrointestinal immune barrier: impact via gut microbiota and direct effects on immune cells

Pectins are dietary fibers with different structural characteristics. Specific pectin structures can influence the gastrointestinal immune barrier by directly interacting with immune cells or by impacting the intestinal microbiota. The impact of pectin strongly depends on the specific structural characteristics of pectin; for example, the degree of methyl-esterification, acetylation and rhamnogalacturonan I or rhamnogalacturonan II neutral side chains. Here, we review the interactions of specific pectin structures with the gastrointestinal immune barrier. The effects of pectin include strengthening the mucus layer, enhancing epithelial integrity, and activating or inhibiting dendritic cell and macrophage responses. The direct interaction of pectins with the gastrointestinal immune barrier may be governed through pattern recognition receptors, such as Toll-like receptors 2 and 4 or Galectin-3. In addition, specific pectins can stimulate the diversity and abundance of beneficial microbial communities. Furthermore, the gastrointestinal immune barrier may be enhanced by short-chain fatty acids. Moreover, pectins can enhance the intestinal immune barrier by favoring the adhesion of commensal bacteria and inhibiting the adhesion of pathogens to epithelial cells. Current data illustrate that pectin may be a powerful dietary fiber to manage and prevent several inflammatory conditions, but additional human studies with pectin molecules with well-defined structures are urgently needed.Subject terms: Mucosal immunology, Translational immunology     

Photocycloaddition of Six‐Membered Cyclic Enones to Propen‐2‐yl Isocyanate

On irradiation in the presence of propen‐2‐yl isocyanate ( 4 ), six‐membered cyclic enones 3 are converted into regio‐ and stereoisomeric mixtures of [2+2] cycloadducts 5 – 10 ; the preferentially formed HT products, 5 – 8 , can be converted into the corresponding bicyclic amines by acid hydrolysis, whereas, under these conditions, the regioisomeric HH‐isocyanato derivatives undergo a retro‐Mannich reaction.