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  • 1980-1984  (8)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 325 (1983), S. 729-741 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XVIII. 2-Alkoxy-2H-pyrans from Tetra- and Pentasubstituted Pyrylium SaltsAlkali alkoxides add regioselectively to 2,3,4,6-tetrasubstituted pyrylium salts 7 (R'= H), affording high yields of colourless crystalline 2-alkoxy-2H-pyrans 9. The latte are also formed simply on refluxing 7 in the corresponding alcohol with triethylamine as proton acceptor. 3,5-Dialkylsubstituted 2,4,6-triarylpyrylium salts react analogously. The 2H-pyran structure of the adducts obtained follows from their n.m.r., i.r., u.v. and mass spectra as well as from their reaction with tetracyanoethylene to cycloadducts of type 10. Acids regenerate from 9 the original pyrylium cations, whereas reaction of 9 with nitromethane or ethyl cyanoacetate provides benzene derivatives. -- The novel starting pyrylium salts 7b--o are characterized by u.v./vis data and by transformation into the corresponding pyridine derivatives
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 326 (1984), S. 955-961 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXV. Quantum Chemical Calculations Concerning the Valence Isomerization of 2-Amino-2H-pyran and -thiopyranThe equilibrium 2-amino-2H-pyran 6 ⇌ 5-amino-2,4-dien-1-one 7 was investigated using the semi-empirical MINDO/3 and MNDO methods. In accordance with experimental findings for the substituted derivatives 1/2a-d, the introduction of a methyl group into the position 3 of 6 or the exchange of oxygen by sulfur shifts the equilibrium towards the cyclic structures 8 and 10, respectively. Polar solvents, the influence of which was estimated applying the reaction field approach as well as the solvaton theory, and entropy effects are calculated to favour the ring-open valence isomer 7. These results also correspond to experimental results.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 326 (1984), S. 287-302 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXI. Structure and Tautomerism of Pseudobases of Unsymmetrically Substituted 2,4,6-Triarylpyrylium SaltsHydrolytic ring opening of unsymmetrically substituted 2,4,6-triarylpyrylium salts 11 results in a mixture of two tautomeric pseudobases, the penten-1,5-diones 13 and 14. In crystalline state as a rule one of these tautomers markedly predominates, whereas in solution a rapid equilibrium establishment occurs which can be followed by 1H-n.m.r. and u.v. spectroscopy (equilibrium ratio nearly 1:1). The 1H-n.m.r. spectroscopic structural assignment of the two isomeric forms was supported by u.v. spectroscopic studies using 1:1 mixtures of the chromophoric partial systems ArCOCH=CHPh and ArCOMe or the pseudobases 10 of symmetrically substituted 2,4,6-triarylpyrylium salts 9 as reference systems. From the mass spectra of the pseudobases 10 and 13/14 follows that - if hydrolysis of 11 is performed in media containing H218O - mass spectrometric isotopic analysis of the resulting 18O-labelled pseudobases allows no information to be made about the regioselectivity of the ring opening. - Novel starting pyrylium salts of type 9 and 11 are characterized by u.v./vis data and by transformation into the corresponding pyridine derivatives.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 326 (1984), S. 647-656 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXII. 1H-N.M.R. and U.V. Spectroscopic Investigations on the Isomerization of Pseudobases of Unsymmetrically Substituted 2, 4, 6-Triarylpyrylium SaltsThe kinetics and mechanism of the isomerization of the title compounds, the pentene 1,5-diones 2 and 3, were studied by 1H-n.m.r. and u.v. spectroscopy. The equilibrium constants measured vary little near 1, indicating the small influence of substituents on the equilibrium position. The mutual rearrangement 2⇄3 proved to be a base-catalized reaction which is characterized by strictly linear Hammett correlation between 1g k and Σσp. The results obtained suggest resonance-stabilized anions of type4 as intermediates. - Pseudobases of 3-alkyl-2, 4, 6-triarylsubstituted pyrylium salts do not undergo a reversible isomerization.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 322 (1980), S. 229-236 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Phosphorus Compounds. XIII. Reaction of Vinylogous Chloromethylene Immonium Salts with Trialkyl Phosphites3-Chloropropenylidene immonium salts of the type Cl—CAr=CH—CH=NMe2⊕X⊖ don't react like chloromethylene immonium salts Cl—CH=NMe2⊕X⊖ with trialkyl phosphites according to the classical MICHAELIS-ARBUSOV principle (RO)3P + R′Cl → (RO)2P(O)R′ + RCl but lead to salts of 1-dimethylaminophosphonates (RO)2P(O)—CH(NMe2 · HX)—CH=CClAr the structure of which is confirmed by two independent syntheses. Some characteristic reactions of the free dimethylaminophosphonates are described.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 322 (1980), S. 99-124 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylogous Acyl Compounds. XIX. Vinylogous Acyl Group Migration in 2-Aminophenol. A Contribution to the Isomerization Mechanism of Mixed Diacyl Derivatives of 2-AminophenolStarting with 2-acylaminophenols 5 and 2-(2-acylvinylamino)-phenols 6 the N-acyl O-acylvinyl derivatives 7 of 2-aminophenol and their N-acylvinyl O-acyl isomers 8 were prepared and characterized. These vinylogous acyl compounds are able to isomerize in the same manner as simple O,N-diacylated 2-aminophenols 3 and 4, which under suitable conditions easily rearrange to give a dynamic equilibrium 3 ⇌ 4. Contrary to 3 and 4, however, the isomerization of 7 and 8 can be followed directly by spectroscopic methods, so that vinylogs of this type are useful model systems for studying acyl group migrations in 2-aminophenol. Kinetic measurements show that the mutual rearrangement of 7 and 8 is a reversible general based catalyzed reaction, being first order with respect to substrate and catalyst. The isomerization of the N-acetyl derivatives 7a-h as well as the N-benzoyl derivatives 7i-p results in strictly linear HAMMETT correlations with positive reaction constants ϱ. In the case of 7a-h the equilibrium constant K and the forward and reverse velocity constants k1 and k2 (including activation parameters) could be determined. The kinetic investigations and additional nonkinetic experiments indicate that the catalyst acts as proton acceptor and not  -  as hitherto supposed  -  as acyl group transferring nucleophile. Based on the findings an isomerization mechanism for mixed diacyl derivatives of 2-aminophenol is suggested.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 324 (1982), S. 1063-1068 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Phosphorus Compounds. XIV. Studies on the Reactivity of Pesticidal Phosphoramidothioate Dimethyl Esters
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 325 (1983), S. 55-65 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylogous Acyl Compounds. XX. Reactivity and Toxicity of Aryl-substituted β-Chlorovinyl Ketones, β-Chlorovinyl Aldehydes, and β-Chlorovinyl Methyleniminium SaltsBased on kinetic measurements, the nucleophilic replaceability of the chlorine in aromatic β-chlorovinyl ketones ArCO-CH = CH-Cl (1), isomeric β-chlorovinyl aldehydes OCH—CH=C(Cl)Ar(2), and corresponding β-chlorovinyl methyleniminium salts Me2N⊕;=CH—CH=C(Cl)Ar X⊖ (3) is compared and related to toxicological findings. The chemical reactivity of these important synthetic building blocks increases in the order 2〈1〈3, the acute toxicity (24 h LD50 i. p. in the mouse) shows the graduation 2〈3〈1. Compounds of type 1 prove to be relatively toxic (LD50 24-42 mg/kg) and display a marked necrotic action after percutaneous absorption, whereas the aldehydes 2 have not only a minor acute toxicity (LD50 158-298 mg/kg) but also a somewhat less marked skin damaging activity. In addition, the LD50 values of selected β-chlorovinyl carbonyl compounds are compared with those of corresponding halogen-free compounds as well as of vinylogous carbonamidium salts ArCO—CH=CH—N⊕R3X⊖. The latter, which can be used as synthetic equivalents of 1, differ in both the reduced acute toxicity and missing skin damaging properties.
    Additional Material: 4 Tab.
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  • 9
    Publication Date: 2023-09-19
    Description: Eastern Boundary Upwelling Ecosystems (EBUEs) are associated with high biological productivity, high fish catch and they highly contribute to marine carbon sequestration. Whether coastal upwelling has intensified or weakened under climate change in the past decades is controversially discussed and different approaches (e.g., time-series of chlorophyll, wind, sea surface temperature, modeling experiments) have been considered. We present a record of almost two decades of particle fluxes (1991–2009) from ca. 600 to 3100 m water depth in the Canary Basin at site ESTOC (European Station for Time series in the Ocean Canary Islands; ca. 29°N, 15°30.W, ca. 3600 m water depth), located in the offshore transition zone of the northern Canary Current-EBUE. We compare these flux records with those measured at a mesotrophic sediment trap site further south off Cape Blanc (Mauritania, ca. 21°N). The deep ocean fluxes at ESTOC in ca. 3 km recorded the evolution of the coastal Cape Ghir filament (30–32°N, 10–12°W) due to lateral advection of particles, whereas the upper water column sediment traps in ca. 1 km reflected the oligotrophic conditions in the overlying waters of ESTOC. We observed an increased emphasis in spring-time fluxes since 2005, associated with a change in particle composition, while satellite chlorophyll biomass did not show this pattern. Due to its northern location in the CC-EBUEs, spring biogenic fluxes at ESTOC provide a better relationship to the forcing of the North Atlantic Oscillation than those recorded further south off Cape Blanc. Off Cape Blanc, deep fluxes showed the best overlap with the deep ESTOC fluxes during the spring season before 2005. On the long-term, both chlorophyll and particle fluxes showed an increasing trend at ESTOC which was not observed further south at the mesotrophic Cape Blanc site. This might indicate that, depending on their location along the NW African margin, coastal upwelling systems react differently to global change.
    Type: Article , PeerReviewed
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  • 10
    Publication Date: 2024-02-07
    Description: Mesoscale eddies are abundant in the eastern tropical North Atlantic and act as oases for phytoplankton growth due to local enrichment of nutrients in otherwise oligotrophic waters. It is not clear whether these eddies can efficiently transfer organic carbon and other flux components to depth and if they are important for the marine carbon budget. Due to their transient and regionally restricted nature, measurements of eddies' contribution to bathypelagic particle flux are difficult to obtain. Rare observations of export flux associated with low-oxygen eddies have suggested efficient export from the surface to the deep ocean, indicating that organic carbon flux attenuation might be low. Here we report on particle flux dynamics north of the Cabo Verde islands at the oligotrophic Cape Verde Ocean Observatory (CVOO; approx. 17∘35′ N, 24∘15′ W). The CVOO site is located in the preferred pathways of highly productive eddies that ultimately originate from the Mauritanian upwelling region. Between 2009 and 2016, we collected biogenic and lithogenic particle fluxes with sediment traps moored at ca. 1 and 3 km water depths at the CVOO site. From concurrent hydrography and oxygen observations, we confirm earlier findings that highly productive eddies are characterized by colder and less saline waters and a low-oxygen signal as well. Overall, we observed quite consistent seasonal flux patterns during the passage of highly productive eddies in the winters of 2010, 2012 and 2016. We found flux increases at 3 km depth during October–November when the eddies approached CVOO and distinct flux peaks during February–March, clearly exceeding low oligotrophic background fluxes during winter 2011 and showing an enhanced particle flux seasonality. During spring, we observed a stepwise flux decrease leading to summer flux minima. The flux pattern of biogenic silicate (BSi) showed a stronger seasonality compared to organic carbon. Additionally, the deep fluxes of total mass showed an unusually higher seasonality compared to the 1 km traps. We assume that BSi and organic carbon/lithogenic material had different sources within the eddies. BSi-rich particles may originate at the eddy boundaries where large diatom aggregates are formed due to strong shear and turbulence, resulting in gravitational settling and, additionally, in an active local downward transport. Organic carbon associated with lithogenic material is assumed to originate from the interior of eddies or from mixed sources, both constituting smaller, dust-ballasted particles. Our findings suggest that the regularly passing highly productive eddies at CVOO repeatedly release characteristic flux signals to the bathypelagic zone during winter–spring seasons that are far above the oligotrophic background fluxes and sequester higher organic carbon than during oligotrophic settings. However, the reasons for a lower carbon flux attenuation below eddies remain elusive.
    Type: Article , PeerReviewed
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