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1Author    Johannes Breker, Reinhard Schmutzler, BerndD. Orbath, M. Arkus WieberRequires cookie*
 Title    Reaktionen von unsymmetrischen A5P -A 3P-Diphosphorverbindungen und von Diphosphinen (A3P -A 3P) mit ö-Chinonen Reactions of Unsymmetrical /i5P -/ 3P D iphosphorus Compounds and of Diphosphines (>l3P -A 3P) with o-Quinones  
 Abstract    The reaction o f A5P -x 3P diphosphorus com pounds with o-quinones, e.g. tetrachloro-o-benzoquinone or 2,5-di-te/7-butyl-o-benzoquinone, led not only to oxidative addition o f the o-quinone to A3P but also to insertion o f a further molecule o f o-quinone into the P -P bond (i.e. x5P -Ä 3P diphosphorus com pound and o-quinone reacted in a molar ratio 1:2). In the course o f these oxidative addition and insertion reactions the o-quinones were converted into the corresponding hydroquinones (i.e. catechols). The products o f these reactions were charac­ terized by N M R and mass spectrometric methods, and by elemental analysis. The hydrolysis o f the 1:2 addition products proceeded with cleavage o f a P -O -C (hydroquinone) bond and formation o f mononuclear products, involving Ä4P and A5P, respectively. A mechanism o f this hydrolysis is proposed and has been elucidated by independent synthesis o f some products. Diphosphines, i.e. symmetrical A3P -z 3P diphosphorus compounds, were found to react with o-quinones in the same fashion in a molar ratio 1:3, i.e. with oxidative addition o f the o-quinone to both x3P atom s and insertion o f tetrachloro-o-catechol into the P -P bond. 
  Reference    Z. Naturforsch. 45b, 1177—1186 (1990); eingegangen am 13. Oktober 1989 
  Published    1990 
  Keywords    Phosphoranes, Insertion, Oxidative Addition 
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 TEI-XML for    default:Reihe_B/45/ZNB-1990-45b-1177.pdf 
 Identifier    ZNB-1990-45b-1177 
 Volume    45 
2Author    Anastassios Zografidis, Kurt Polborn, Wolfgang Beck, BertusA. Markies, G. Erard, Van KotenRequires cookie*
 Title    Insertion of Isocyanides into the Palladium-Carbon Bond of Cyclopalladated Complexes  
 Abstract    Insertion of isocyanides into the P d -C bond has been observed in the reactions of PdBr[C6H3(CH2NMe2)2-2,6] with isocyanides CNR which give the complexes 
  Reference    Z. Naturforsch. 49b, 1494—1498 (1994); received June 27 1994 
  Published    1994 
  Keywords    Palladium Complexes, Isocyanide, Cyclopalladation, Insertion 
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 TEI-XML for    default:Reihe_B/49/ZNB-1994-49b-1494.pdf 
 Identifier    ZNB-1994-49b-1494 
 Volume    49 
3Author    Wolfgang Malisch, Katharina Thirase, Joachim ReisingRequires cookie*
 Title    Ubergangsmetall-substituierte Phosphane  
 Abstract    , Arsane und Stibane, LX [1]. Ferrio-(thiocarbamoyl)phosphane Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R = Me, Et, f-Bu): Aufbau aus dem Ferrio-mesitylphosphan Cp(OC)2Fe-P(Mes)H und Organoisothiocyanaten sowie Quaternisierung mit Alkylhalogeniden und Oxidation mit Schwefel Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LX [1]. Ferrio-(thiocarbamoyl)phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R= Me, Et, r-Bu): Build-up from the Ferrio-mesitylphosphane Cp(OC)2Fe-P(Mes)H and Organoisothiocyanates, Quatemization with Alkyl Halides and Oxidation with Sulfur The ferrio-phosphane Cp(OC)2Fe-P(Mes)H (4), obtained by deprotonation of the me-sitylphosphane iron complex {Cp(OC)2 [H2(Mes)P]Fe}BF4 (3), reacts with the organoiso­ thiocyanates RNCS (R = Me, Et, Ph) (5a -c) to give the functionalized ferrio-phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (6a-c). Quatemization of 6a,b at the phosphorus atom with the alkyl halides R'-Hal (R1 = Me, Et, CH2 Ph) (7a-c) yields the complexes {Cp(OC)2Fe-P(Mes)(R')[C(=S)-N(H)(R)]}Hal (8a-d), whereas oxidation with elemental sulfur affords the ferrio-thiophosphoranes Cp(OC)2Fe-P(=S)(Mes)[C(=S)-N(R)H] (R = Me, Et) (10a,b). 10b is alkylated with Mel to give {Cp(OC)2Fe-P(SMe)(Mes)[C(=S)-N(Et)H]}I (11). The structure of 8b has been determined by X-ray analysis. 
  Reference    Z. Naturforsch. 53b, 1084—1091 (1998); eingegangen am 12. Mai 1998 
  Published    1998 
  Keywords    Metallo-Phosphanes, Insertion, Quatemization, Oxidation 
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 TEI-XML for    default:Reihe_B/53/ZNB-1998-53b-1084.pdf 
 Identifier    ZNB-1998-53b-1084 
 Volume    53 
4Author    Berthold Kersting, Michael DelionRequires cookie*
 Title    Synthesis of Benzisochalcogenol and -azole Derivatives via ortho Metalation of Isophthalamides  
 Abstract    The syntheses of benzofused isochalcogenazole derivatives via orf/?o-lithiation of isophtha­ lamides is reported. AUV'-Dialkyl-isophthalamides, C6H4-l,3-(CONHR)2, bearing R = /Pr or fBu substituents are readily ortho metalated by using 3.3 equiv. of «-BuLi/TMEDA. The organo lithium compounds react with S, Se, or Te to give 2-chalcogenol-isophthalamides, C 6 H v l,3 -(CONHR)2-2-XH (X = S, Se, Te). Oxidation of the chalcogenols affords dichalcogenides under acidic and benzisochalcogenazoles under basic conditions, respectively. The formation of the five-membered heterocycles proceeds by disproportionation of the dichalcogenides. Oxidation of the benzisothiazoles by hydrogen peroxide gives access to substituted sulfin-and sulfon­ amides. 
  Reference    Z. Naturforsch. 54b, 1042—1047 (1999); received June 1 1999 
  Published    1999 
  Keywords    Isophthalamides, Metalation, Chalcogen, Insertion, Oxidation 
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 TEI-XML for    default:Reihe_B/54/ZNB-1999-54b-1042.pdf 
 Identifier    ZNB-1999-54b-1042 
 Volume    54 
5Author    Helmut Fischer, Claudia Kalbas, C. Arsten, Troll, KlausH. FluckRequires cookie*
 Title    Regiospezifische Insertion von [SCN]" und [SeCN]-in die S -C -bzw. Se-C-Bindung Übergangsmetall-koordinierter Thietane und Selenetane Regiospecific Insertion of [SCN] and [SeCN] in the S -C -and S e-C -B ond of Transition-M etal-Coordinated Thietanes and Selenetanes  
 Abstract    Pentacarbonyl(thietane)tungsten complexes react with thiocyanate, [SCN]", and S i0 2/H 20 by insertion of the CN group into a S -C bond o f the four-membered heterocycle, 1,3-migra­ tion of the pentacarbonyltungsten fragment and protonation o f the nitrogen atom to give tungsten-coordinated thiazinthione complexes. Analogously, the reactions of a thietane tung­ sten complex with [SeCN]-and S i0 2/H 20 affords a thiazinselone complex. A selenazinthione complex is obtained from a selenetane complex and [SCN]-(+ S i0 2/H 20). The insertions are regiospecific and stereoselective. The structure of the /rarcs-isomer o f a pentacarbonyl-(thiazinthione) complex has been established by X-ray structure analysis. 
  Reference    Z. Naturforsch. 48b, 1613—1620 (1993); eingegangen am 23. Juni 1993 
  Published    1993 
  Keywords    Thietane Complexes, Selenetane Complexes, Insertion, Thiazinchalcone Complexes, Selenazinthione Complex 
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 TEI-XML for    default:Reihe_B/48/ZNB-1993-48b-1613.pdf 
 Identifier    ZNB-1993-48b-1613 
 Volume    48