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  • 11
    Electronic Resource
    Electronic Resource
    The wonderful world of organosilicon chemistryAs presented at the Ninth International Symposium on Organosilicon Chemistry, Edinburgh (scotland); July 16-20, 1990. (1991)
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 2 (1991), S. 335-355 
    Details
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hc.520020216
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  • 12
    Electronic Resource
    Electronic Resource
    Structural Studies of Novel Siloxysilsesquioxanes (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1087-1094 
    Details
    ISSN: 1434-1948
    Keywords: Silsesquioxanes ; MALDI-TOF ; DSC ; Structure elucidations ; Thermochemistry ; Mass spectrometry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five silsesquioxanes (RSiO3/2)2n with R = siloxy and n = 4, 5 have been investigated by X-ray crystallography, MALDI-TOF mass spectrometry, and differential scanning calorimetry (DSC).
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Carbon=Carbon Hydrogenation of Silicon-Functionalized Silaheterocycles (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1095-1102 
    Details
    ISSN: 1434-1948
    Keywords: Silanorbornenes ; Silanorbornanes ; Silicon-functionalized olefins ; Silacyclobutanes ; Hydrogenations ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Catalytic hydrogenation of olefins containing functionalized silicon groups affords the saturated products in good yields. Chloro and alkoxy substituents at the silicon atom remain unaffected and, in the case of heterocyclic compounds, the cyclic or bicyclic moieties remain intact. The 2-silanorbornanes 4, 5, and 6 were synthesized from the corresponding 2-silanorbornenes 1, 2, and 3, and organosilanes 13 and 14 possessing the cyclopentyl group, were prepared from the cyclopentenyl-substituted precursors 10 and 12. The 3-vinyl-substituted silacyclobutanes 15, 17, and 18 were also hydrogenated in a simple apparatus with diethyl ether or THF as solvent, and Pd/C as a recoverable catalyst system. A basic organosilicon compound, trichloro(vinyl)silane, is hydrogenated in a nearly quantitative yield to form the saturated trichloro(ethyl)silane; this emphasizes the general applicability of this method.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    Towards 2-Silaallenes: Synthesis of Spirocyclic PrecursorsSilaheterocycles part 34. For part 33, see N. Auner, C. R. Heikenwälder, Z. Naturforsch., in press. (1997)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 948-957 
    Details
    ISSN: 0947-6539
    Keywords: cycloadditions ; silaallenes ; silicon ; small ring systems ; spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of dichlorodivinylsilane (2) and LitBu in a molar ratio 1/1 and 1/2 lead to highly reactive intermediates, which can be trapped by suitable reagents. In the presence of trimethylmethoxysilane, norbornadiene, anthracene and diphenylacetylene, products are formed that provide evidence for the intermediate formation of both the neopentylsilene H2C=CH(Cl)Si=CHCH2tBu (3) and the 2-silaallene tBuCH2CH=Si=CHCH2tBu (4). The formation of double cycloadducts from 4 is particularly interesting as a preparatively facile route for the synthesis of silaspirocycles such as 13, 16 and 17, which have been characterized by single-crystal X-ray structure analysis.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19970030617
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  • 15
    Electronic Resource
    Electronic Resource
    Organosilicium-Chemie: Vom Molekül zum WerkstoffHerrn Prof. Dr. K. Rühlmann zum 65, Geburtstag gewidmet. (1995)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 337 (1995), S. 79-92 
    Details
    ISSN: 0941-1216
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organosilicon Chemistry: From Molecules to MaterialsThe transition from basic to applied organosilicon chemistry is described for the research fields that are studied by the author's group: silaethene chemistry, organosilicon polymer chemistry with silacycles and the chemistry of higher coordinated silicon species.Early investigations started with the study of the pyrolysis of silacyclobutanes that yielded silaethenes in the gas phase. However, these investigations are tedious and are of little use for a widespread study of silaethene chemistry. Therefore the generation of silaethenes in solution (from vinylchlorosilanes and tert-butyllithium) is the preferred method. Numerous differently substituted silaethenes have been generated in situ and their reactivity, especially in cycloaddition reactions, has been studied. Silaethenes that have two chlorine substituents at the silicon atom (especially Cl2Si=CHCH2But) show an unusual cycloaddition reactivity and yield unexpected products with dienes and trienes (e. g. from [2+2] and [6+2] reactions); some of the silenes with donorfunctional groups at the α-C-atom undergo interesting intramolecular rearrangements. The cycloadducts of Si-dichlorofunctional silenes also show rearrangements when thermolyzed (e. g. [2+2] → [4+2] adducts). The reactivity of these silaethenes and their cyclo-adducts is due to the two chlorine atoms at the silicon atom and their influence can be explained by theoretical models.Silacycles synthesized from silaethenes have been incorporated or have been transformed into silicon containing polymers. Model compounds for nucleophilic substitution reactions at silicon centers and for the hydrolysis of chlorosilanes are higher coordinated silicon species up to coordination number „seven“. Some structures that describe such reactions have been characterized by X-ray crystallography.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19953370121
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  • 16
    Electronic Resource
    Electronic Resource
    Silaheterocyclen, XXII. Diels-Alder-Reaktionen von Dichlor(neopentyl)silaethen mit Furanen und Umlagerung der erhaltenen Bicyclen zu monocyclischen Si - O-Siebenring-Verbindungen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 575-580 
    Details
    ISSN: 0009-2940
    Keywords: Silaethene derivatives ; Furans ; Cycloaddition reactions ; Rearrangements ; Sila heterocycles ; Diels-Alder reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sila Heterocycles, XXII[1]. - Diels-Alder Reactions of Dichloro(neopentyl)silaethene with Furans and Rearrangement of the Resulting Bicycles into Monocyclic Si - O Seven-Membered Ring compoundsThe reaction of trichloro(vinyl)silane (1) and LitBu (2) initially leads to the α1-lithio adduct Cl3SiCH(Li)CH2tBu (3) which can be trapped by trimethylsilyl triflate yielding the C1-silylated product [Cl3SiCH(SiMe3)CH2tBu (5)]. 1,2-LiCl elimination from 3 gives dichloro(neopentyl)silaethene [Cl2Si=CHCH2tBu (4)] as intermediate. This can be established by insertion of 4 into the Si - O bond of Me3SiOMe to Cl2Si(OMe)CH(SiMe3)CH2tBu (6). 4 is a dienophile of high activity and reacts with the furans 7 - 9 to give the [4 + 2] cycloaddition compounds 10 - 12. These Diels-Alder products are thermally unstable and decompose slowly at room temperature into the starting furans and tetrachlorodisilacyclobutane (15). Under thermolysis conditions (3 d/17°C) they rearrange into the monocyclic Si - O seven-membered ring compounds 16 - 18. A mechanism for the 7-Oxa-2-silabicyclo[2.2.1]hex-5-en → 1-Oxa-2-silacyclohepta-4,6-diene rearrangement is proposed.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260305
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  • 17
    Electronic Resource
    Electronic Resource
    Silaheterocyclen, XXV. (Me3SiO)2Si—CHCH2tBu: Ein Siloxy-funktionalisiertes Syntheseäquivalent für DichlorneopentylsilaethenHerrn Prof. Dr. U. Wannagat zum 70. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2177-2186 
    Details
    ISSN: 0009-2940
    Keywords: Silene, neopentyl- ; Me3SiO substituents ; Cycloaddition reactions ; Silaethene derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silaheterocycles, XXV[1].  -  (Me3SiO)2Si—CHCH2tBu: A Siloxy-Functionalized Synthetic Equivalent for Dichloroneopentylsilene(Me3SiO)2Si—CHCH2tBu (4) is obtained by the reaction of (Me3SiO)2Si(Cl)CH=CH2 (2) with LitBu. The reaction proceeds via the α-lithiated species 3, which can be intercepted by trimethylsilyl triflate to give 5. Silaethene 4 dimerizes to the E/Z-isomers of disilacyclobutane 7 and adds to Me3SiOMe to give 6. The reactivity of 4 resembles that of Cl2Si—CHCH2tBu (1): A [4 + 2] cycloadduct is obtained from the reaction with anthracene, and with 1,3-cyclohexadiene and 1,3-cycloheptadiene mixtures of monosilacyclobutanes (10 and 12) and bicyclic Diels-Alder adducts (9 and 11) are available. Exclusive [2 + 2] cycloaddition reactions take place with styrene (formation of 13), 2,3-dimethyl-1,3-butadiene (→19), and 1,3-butadiene (→21). With quadricyclane only the product (14) originating from a [2 + 2 + 2] cycloaddition is formed, while with 2,5-norbornadiene the [2 + 2] and [2 + 2 + 2] cycloadducts (14 and 15) are formed. In addition the ene products (16, 18, 20, 22) are isolated in some cases from side reactions.  -  The tendency of 1 and 4 to preferably participate in [2 + 2] cycloaddition reactions is ascribed to the polarity of the Si—C bond and the additional influence of the π donor ligands at silicon. These factors enable a stepwise [2 + 2] reaction in which the primary zwitterionic intermediates B are cyclized to yield the SiC four-membered ring compounds.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931261004
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  • 18
    Electronic Resource
    Electronic Resource
    Silaheterocyclen, XXIII. Synthese und Thermolyseverhalten von Si-funktionellen 2-Silaazetidinen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 581-589 
    Details
    ISSN: 0009-2940
    Keywords: Silene, dichloroneopentyl- ; Imines ; Cycloaddition reactions ; 2-Silaazetidines ; Thermolysis reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silaheterocycles, XXIII[1]. - Synthesis and Thermolysis Reactions of Si-Functionalized 2-SilaazetidinesDichloroneopentylsilene (1) is formed in situ by the reaction of trichlorovinylsilane with LitBu. The [2 + 2] cycloaddition to imines yields Si, Si1-dichloro-functionalized 2-silaazetidines in a preparative scale. With aldimines as trapping agents for 1, the resulting SiN four-membered ring compounds are isolated as syn/anti1-isomers (e.g. syn/anti-15 and -16; syn/anti ≍ 2:1). Silene 1 is not liberated from the silaazetidines on heating, but the Si, Si1-dichloro-substituted silanimine Cl2Si=NtBu (24) is formed. This can be trapped by Me3SiOMe or Ph2C=NtBu to give the addition products 25 and 26, respectively. The pathways are discussed which lead to stereoisomeric SiN ring compounds by a multiple-step mechanism including zwitterionic intermediates (1,4-dipoles). In addition there is strong evidence for the formation of 1, depending on the trapping reagent used. This fact may be explained by donor→silene interactions. The thermolysis products of silaazetidines support the formulation of a stepwise decomposition to an alkene and Cl2Si=NR derivatives.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260306
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  • 19
    Electronic Resource
    Electronic Resource
    Neue Naphthalin- und Cyclohexa-1,3-dien-Silaethen-CycloaddukteSilaheterocyclen, 10. Mitteilung. Diese Arbeit wurde von der Volkswagen-Stiftung, der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie gefördert.  -  9. Mitteilung: [11]. (1991)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 103 (1991), S. 425-426 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19911030411
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  • 20
    Electronic Resource
    Electronic Resource
    Einfache Synthese von Si-funktionellen SilacyclobutenenSilaheterocyclen, 12. Mitteilung. Diese Arbeit wurde von der Volkswagen-Stiftung, der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie gefördert. - 11. Mitteilung: [15]. (1991)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 103 (1991), S. 1172-1173 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19911030927
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