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  • Chemistry  (15)
  • JGOFS; Joint Global Ocean Flux Study; Polar_Front_1; SFB261; South Atlantic in Late Quaternary: Reconstruction of Budget and Currents; Trap; TRAP; WS3_trap; WS4_trap  (1)
  • formal specifications
  • 1990-1994  (3)
  • 1985-1989  (14)
Collection
Keywords
Publisher
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Domain-oriented design environments (1994)
    Springer
    Automated software engineering 1 (1994), S. 177-203 
    Details
    ISSN: 1573-7535
    Keywords: automatic programming ; cooperative problem solving ; co-evolution of specification and construction ; critiquing ; design ; domain-oriented design environments ; design rationale ; end-user modifiability ; evolution ; FRAMER ; formal specifications ; JANUS ; knowledge-based software assistant ; languages of doing ; software reuse and redesign ; stakeholders ; upstream and downstream activities
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract The field of knowledge-based software engineering has been undergoing a shift in emphasis from automatic programming to human augmentation and empowerment. In our research work, we support this shift with an approach that embedshuman-computer cooperative problem-solving tools intodomain-oriented, knowledge-based design environments. Domain orientation reduces the large conceptual distance between problem-domain semantics and software artifacts. Integrated environments support the coevolution of specification and construction while allowing designers to access relevant knowledge at each stage within the software development process. This paper argues thatdomain-oriented design environments (DODEs) are complementary to the approaches pursued withknowledge-based software assistant systems (KBSAs). The DODE extends the KBSA framework by emphasizing a human-centered and domain-oriented approach facilitating communication about evolving systems among all stakeholders. The paper discusses the major challenges for software systems, develops a conceptual framework to address these problems, illustrates DODE with two examples, and assesses the contributions of the KBSA and DODE approaches toward solving these problems.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00872289
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  • 2
    Electronic Resource
    Electronic Resource
    Photochemische Umwandlungen, 64. Die 3σ → 3π-Route zu Oxepinen/Benzoloxiden (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 589-615 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemical Transformations, 64. The 3σ → 3π-Route to Oxepines/Benzene OxidesThe 7-oxanorbornadiene skeleton (8a), its 2,3-bis(trifluoromethyl) derivative (8b), and several 2,3-dicarboxylic esters with potential dipolarophilic groups at C-1 (16a - d, 17a - c) were synthesized and selectively transformed into the 3-oxaquadricyclanes (18a,b, 19a - d, and 20a - c) through sensitized (8a,b) or direct (16a - d, 17a - c) photoexcitation. In the thermolysis of these oxaquadricyclanes [18a(b): Ea(C6D6) = 32.6 ± 0.3 kcal/mol (32.2 ± 1.4 kcal/mol); lg A = 15.8 (14.5)] CF3(CH3CO2) substituents at C-2(3) favor the scission of the opposite (neighbouring) cyclopropane bonds. Competition experiments with dimethyl acetylenedicarboxylate as external dipolarophile support the stepwise mechanism of the oxaquadricyclane → oxepine conversion. The intramolecular carbonyl ylide-interception cannot compete with oxepine formation in 19a - d but is efficient in 20a - c. The unusually low activation barrier (Ea(C6D6) = 23.5 ± 1 kcal/mol; lg A = 11.6) and singular specifity in case of 20a is interpreted in terms of a concerted [π2 + σ2 + σ2]-cycloaddition to the bishomofuran unit of the oxaquadricyclane skeleton.
    Notes: Das 7-Oxanorbornadien-Grundgerüst (8a), das 2,3-Bis(trifluormethyl)-Derivat (8b) und diverse 2,3-Dicarbonester mit potentiell dipolarophilen Gruppen an C-1 (16a - d, 17a - c) wurden synthetisiert und durch sensibilisierte (8a,b) bzw. direkte Lichtanregung (16a - d, 17a - c) durchweg hochselektiv in die 3-Oxaquadricyclane (18a,b, 19a - d, 20a - c) umgewandelt. Bei der Thermolyse dieser Oxaquadricyclane [18a(b): Ea(C6D6) = 32.6 ± 0.3 kcal/mol (32.2 ± 1.4 kcal/mol); lg A = 15.8 (14.5)] begünstigen CF3(CH3CO2)-Reste an C-2(3) die Spaltung der gegenüberliegenden (benachbarten) Cyclopropanbindungen. Durch Konkurrenzversuche mit Acetylendicarbonsäure-dimethylester als externem Dipolarophil wird der Mehrstufen-Mechanismus der Oxaquadricyclan → Oxepin-Isomerisierung untermauert. Die intramolekulare Carbonylylid-Abfangreaktion kann in 19a - d nicht, wohl aber in 20a - c mit der Oxepinbildung konkurrieren. Deren im Falle von 20a außergewöhnlich niedrige Aktivierungsbarriere (Ea(C6D6) = 23.5 ± 1 kcal/mol; lg A = 11.6) und singuläre Spezifität werden im Sinne einer konzertierten [π2 + σ2 + σ2]-Cycloaddition an die Bishomofuran-Einheit des Oxaquadricyclan-Gerüstes interpretiert.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190222
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  • 3
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen, XXVI. Vergleichende UV/Vis-spektroskopische Untersuchungen an 3-Methyl-2,4,6-triaryl-pyrylium-perchloraten (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 151-155 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXVI. Comparative U.V./Vis. Studies on 3-Methyl-2,4,6-triarylpyrylium Perchlorates
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270122
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  • 4
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. 34 [1] 2-Acetonyl-2H-thiopyrane aus 2,4,6-Triaryl-thiopyryliumsalzen (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 573-581 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. 34. 2-Acetonyl-2H-thiopyrans from 2,4,6-Triarylthiopyrylium Salts2,4,6-Triarylthiopyrylium salts 4 react with acetone in the presence of amine salts of weak acids (e.g. piperidine acetate) to give the hithero unknown 2-acetonyl-2-H-thiopyrans 5, the structure of which was established by spectroscopic methods. Depending on the nature of the amine salt used, the enamine 6 or the enol 7 of acetone may function as attacking nucleophile. Using the 2,4,6-triphenyl derivative 5a as model compound, some typical reactions of 2-acetonyl-2H-thiopyrans were studied. With 2,4-dinitrophenylhydrazine, semicarbazide and thiosemicarbazide, the carbonyl derivatives 10a-c are formed. Hydrogen peroxide in acetic acid affords the S,S-dioxide 11. Methanolic sodium methoxide or sodium hydroxide in aqueous ethanol give rise to a ring transformation yielding 1,3,5-triphenylbenzene (12) and 2,4,6-triphenylacetophenone (13). Under similar conditions, benzaldehyde reacts with 5a to give 2′, 4′, 6′-triphenylchalcone (14). Perchloric acid regenerates from 5a the initial thiopyrylium perchlorate 4a.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280417
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  • 5
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. 30. C-Alkylierung von 1,3,5-Triaryl-penten-1,5-dion-Enolaten: Ein einfacher Zugang zu 3-alkylsubstituierten 2,4,6-Triaryl-pyryliumsalzen (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 983-997 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. 30. C-Alkylation of 1,3,5-Triaryl-pentene-1,5-dione Enolates: A Simple Approach to 3-Alkylsubstituted 2,4,6-Triarylpyrylium Salts1,3,5-Triaryl-pentene-1,5-dione enolates (10), obtainable in crystalline form from 2,4,6-triarylpyrylium pseudobases (9) and sodium methoxide in benzene/ether, react in dipolar aprotonic solvents (e.g. DMSO, DMF) with various types of alkyl iodides to give C-alkylation products (11) which afford 3-substituted 2,4,6-triarylpyrylium salts (12) on treatment with perchloric acid. This reaction sequence proved to be a convenient synthetic route to pyrylium salts (12) having 3-oriented substituents such as normal or branched alkyl groups CnH2n+1 (e.g.n = 1-5), isotopically modified alkyl groups (e.g. C[2H3], C2[2H5]), allyl type substituents (e.g. CH2=CHCH2, MeCH=CHCH2, CH2, CH2=CMeCH2) or benzyl groups (e. g. PhCH2, 4-Br—C6H4CH2). Bifunctional alkylating agents (e.g. 1,4-diiodobutane, o-xylylenediiodide) resulted in a novel type of bispyrylium salts (14) with 3,3′-linkage. The pyrylium salts obtained were characterized by their 1H-n.m.r. and u.v. spectra as well as, in most cases, by transformation into the corresponding pyridine derivatives (13) and bispyridines (15) respectively.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270616
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  • 6
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. XXVII. Spezifisch deuterierte Carbo- und Heterocyclen via 2,4,6-Triaryl-[3,5-2H2]pyryliumsalze (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 529-535 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXVIII. Specifically Deuterated Carbo- and heterocycles via 2,4,6-Triaryl[3,5-2H2]pyrylium SaltsOn heating with catalytic amounts of bases(e.g. triethyl amine) in deuterated alcohols such as methan[2H]ol or ethan[2H]ol pseudobases of 2, 4, 6-triarylpyrylium salts 1 undergo fast1H/2H isotopic exchange reaction affording 1, 3, 5-triaryl[2, 4, 4-2H3]pent-2-ene-1,5-diones which with [2H] perchloric acid give highly deuterated 2, 4, 6-triaryl-[3, 5-2H] pyrylium perchlorates 8. These salts are obtainable also directly from 1 through a one-pot procedure by ring opening of the latter with deuterium oxide under the above-mentioned1H/2H isotopic exchange conditions followed by recyclization of the formed 1, 3, 5-triaryl[2, 4, 4-2H3]pent-2-ene-1, 5-diones with [2H]ClO4. Ring transformations of 2, 4, 6-triphenyl[3, 5-2H2]pyrylium perchlorate (8a) to 2, 4, 6-triphenyl[3, 5-2H2]nitrobenzene (9) 2, 4, 6-triphenyl[3, 5-2H2]pyridine (10), 1, 2, 4, 6-tetraphenyl[3, 5-2H2]pyrydinium perchlorate(11), 2, 4, 6-triphencyl[3, 5-2H2]thiopyrylium perchlorate(12), 2-benzoyl-3, 5-diphenyl[4-2H]furan (13), and 3, 5, 7-triphenyl-[4, 4, 6-2H3]4H-1, 2-diazepin (14) demonstrate the usability of pyrylium salts of type 8 as starting materials for syntheses of specifically deuterated carbo- and hetrocycles.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270402
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  • 7
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. 31 [1]. Reaktion 3-alkylsubstituierter 2,4,6-Triaryl-pyryliumsalze mit 1,3-Diketonaten: Ein Weg zur Darstellung 3-acylsubstituierter Benzophenone (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 359-372 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pyrylium Compounds. 31. Reaction of 3-Alkyl-2,4,6-triarylpyrylium Salts with 1,3-Diketonates: A Method for the Preparation of 3-Acylsubstituted BenzophenonesReaction of 3-alkyl-2,4,6-triarylpyrylium salts with 1,3-diketones in the presence of one equivalent of triethylamine or potassium tert-butoxide does not lead  -  as originally suspected  -  to the primary adducts of 2H-pyran structure 6, but to the open-chain valence isomers 7. Treatment of the latter with one equivalent of tert-butoxide in tert-butyl alcohol gives the same 3-alkyl-2,4,6-triarylacetophenones 9 which are obtained directly from 5, 1,3-diketones and two equivalents of potassium tert-butoxide. However, on treating 7 with aqueous ethanolic sodium hydroxide 3-acylsubstituted benzophenones 10 are formed in good yields. The reaction sequence 5→7→10 can also be performed through a one-pot-procedure.  -  The i.r., u.v., n.m.r. and mass spectroscopic data of the novel products 7, 9, and 10 are reported.
    Notes: No abstract.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280310
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  • 8
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. 32 [1]. 2-Methoxy-2H-thiopyrane aus 2,4,6-Triaryl-thiopyryliumsalzen (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 373-379 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. 32. 2-Methoxy-2H-thiopyrans from 2,4,6-Triaryl-thiopyrylium SaltsReaction of 2,4,6-triarylthiopyrylium salts 1 with sodium methoxide in absolute methanol yields isolable 2-methoxy-2H-thiopyrans 2, the structure of which was proved spectroscopically. Using the 2,4,6-triphenyl derivative 2a as model compound, the behaviour of the 2-methoxy-2H-thiopyran system towards some nucleophiles and electrophiles was studied. Thus, on heating with ethanol the 2-ethoxy-2H-thiopyran 3 is formed. Nitromethane and ethyl cyanoacetate react with 2a in the presence of triethylamine to give 2,4,6-triphenylbenzene (6) and 2,4,6-triphenylbenzonitrile (7), respectively. Electrophiles (e. g. mineral acids or acyl halides) regenerate from 2a the starting thiopyrylium system; the same principle underlies the formation of 2,4,6-triphenylthiopyrylium perchlorate (1a) and 2-methoxy-3-methyl-2,4,6-triphenyl-2H-pyran (5) from 2a and 3-methyl-2,4,6-triphenylpyrylium perchlorate (4).
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280311
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  • 9
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. 33 [1] 2-Dialkylamino-2H-thiopyrane aus 2,4,6-Triaryl-thiopyryliumsalzen (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 567-572 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. 33. 2-Dialkylamino-2H-thiopyrans from 2,4,6-Triaryl-thiopyrylium Salts2,4,6-Triaryl-thiopyrylium salts 7 react with dialkylamines in diethyl ether to give stable crystalline 2-dialkylamino-2H-thiopyrans 8, the structure of which is in accordance with their u.v., n.m.r. and mass spectra. The chemical properties of 8 parallel those of structurally analogous 2-alkoxy- and 2-dialkylamino-2H-pyrans and 2-alkoxy-2H-thiopyrans. Thus, on heating 2-dimethylamino-2,4,6-triphenyl-2H-thiopyran (8a) with methanol the corresponding 2-methoxy-2H-thiopyran 9 is formed. Nitromethane and ethyl cyanoacetate give rise to ring transformations yielding 1,3,5-triphenyl benzene (10) and 2,4,6-benzonitrile (11), respectively. From 8a electrophiles (e.g. mineral acids, methyl iodide, benzoyl chloride) regenerate the initial thiopyrylium system by taking over the dialkylamino group.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280416
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  • 10
    Electronic Resource
    Electronic Resource
    Organische Phosphorverbindungen. XV [1] Reaktivitätsuntersuchungen an ausgewählten Vinylphosphaten (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 651-655 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Phosphorus Compounds. XV. Studies on the Reactivity of Selected Vinyl Phosphates
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280429
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