Search results for "Ethylene"

1967

Enamines derived from cyclic ketones behave as difunctional intermediates when treated with phenyl isocyanate to produce dicarboxanilides. Reaction of bis(4-isocyanatophenyl)-methane with 1-N-morpholino-1-cyclopentene in DMSO leads to poly[iminocarbonyl(2-morpholino-1-cyclopenten-1.3-ylene)carbonylimino-p-phenylenemethylene-p-phenylene], a polyamide. The effects of various cyclic enamines and diisocyanates on the polymerization are surveyed. Morpholine and piperidine are more effective than pyrrolidine or dimethylamine when incorporated into cyclopentanone enamines. The molecular weight of the polymer decreases when the ring size of the ketone component is increased. The efficiency of the d…

Ring-expansion of 5-methylene-thiazolidine-2-thione with hydrazine

2009

On the low-lying singlet excited states of styrene: a theoretical contribution

2000

The present contribution analyses the trans–cis photoisomerization mechanism of ethene and styrene on the singlet manifold. Within the framework of multiconfigurational second-order perturbation theory (CASPT2), the extended multistate approach (MS-CASPT2) is found to be flexible enough to describe energy hypersurfaces adiabatically. For ethene, torsion about the CC bond towards a perpendicular structure leads to a situation where the energy difference between the ground and the lowest excited state is still too large (2.5 eV) for efficient radiationless decay. However, the energy gap decreases to 0.4 eV when one of the methylene moieties is, in addition, pyramidalized from the twisted stru…

Stufenweise Darstellung von Cyclo{quater[(5-alkyl-2-hydroxy-1,3-phenylen)methylen]}en und ihr Vergleich mit linearen phenolischen Mehrkernverbindungen

1978

The stepwise syntheses of cyclo{quater[(5-alkyl-2-hydroxy-1,3-phenylene)methylene]}s (5) are described and compared with a one-flask reaction procedure. The structures of the cyclic compounds 5 are analytically confirmed and their properties were compared with those of linear phenol formaldehyde condensates which have very similar structures and molecular weights.

Topochemische reaktionen von monomeren mit konjugierten dreifachbindungen. II. Mitt.: Eine topochemische farb- und vernetzungsreaktion bei polymeren …

1970

Es wurden kristallisationsfahige Polymere mit zwei konjugierten CC-Dreifachbindungen im Grundbaustein hergestellt und ihre Reaktionsfahigkeit im kristallinen Zustand untersucht. Die Polyurethane aus 2.4-Hexadiin-1.6-diol (I) bzw. 3.6.13.16-Tetraoxa-octadeca-8.10-diin-1.18-diol (II) und Hexamethylendiisocyanat sowie der Polyester aus I und Adipoylchlorid farben sich beim Belichten mit UV-Licht oder beim Tempern unterhalb ihres Schmelzpunktes tief rot und werden dabei unloslich. Die Reaktion kann durch Radikaldonatoren katalysiert und durch Radikalfanger inhibiert werden. Die gelosten Polymeren zeigen keine Reaktivitat in dieser Hinsicht. Die Verfarbung und Vernetzungsreaktion kann in Analogi…

Zur herstellung von carbonylbrücken enthaltenden, phenolischen mehrkernverbindungen

1963

Die bekannte Zweikernverbindung, 6,6′-Dihydroxy-3,3′-dimethyl-benzophenon (I), wurde nach einer geeigneteren Methode hergestellt. Die Darstellung der Dreikernverbindung, 4-Hydroxy-1-methyl-3,5-bis(6-hydroxy-3-methyl-benzoyl-(1))-benzol (IV), gelang mittels einer Friedel-CRAFTS-Synthese. Die Strukturen von I und IV wurden durch Reduktion der Carbonylgruppen und Identifizierung der bekannten, Methylengruppen enthaltenden Zwei- bzw. Dreikernverbindung bewiesen. Einige Vierkernverbindungen mit drei Carbonylgruppen je Molekel konnten durch die Friessche Verschiebung entsprechender Ester von I erhalten werden. The known two-nuclei compound 6,6′-dihydroxy-3,3′-dimethyl-benzophenone (I) was prepare…

Unexpected Conformational Behaviour of a Diphosphate Derived from a Spherand-Type Calixarene

2005

The spherand-type calixarene 2a, which consists of three diphenol units linked by methylene bridges, was treated with phosphorus pentachloride and then with water. A C1-symmetrical conformation was found for the resulting bisphosphate 7 in the crystalline state by X-ray analysis, with an anti orientation of the phosphoryl groups. MM3 calculations lead to a nearly identical conformation for the most stable isomer (RRS-twist), while a slightly higher energy was found for an RRS-crown isomer with a syn orientation of the phosporyl groups. Surprisingly, all NMR studies (1H, 13C and 31P) of 7 are in agreement with a dynamic C2 symmetry in solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Wein…

Syntheses of polyfunctionalized resveratrol derivatives using Wittig and Heck protocols

2012

Improved protocols for Wittig reaction and palladium-catalyzed Heck coupling give expedient access to a series of unprecedented polyfunctionalized artificial-resveratrol derivatives. In the modified Wittig protocol, trimethylsilyl was used as a highly valuable protective group of the phenolic functions of starting aromatic materials. A clean O-alkylation of hydroxylated stilbenes with ethylene carbonate was also conducted. Thus, Wittig reaction followed by hydroxyethylation take place one-pot with only carbon dioxide as waste. Additionally, a palladium-catalyzed Heck coupling strategy was developed by using ferrocenyl phosphane ligands, and multi-functionalized hydroxylated stilbenes were o…

1965

Bei der Polymerisation von Trioxan bei 70°C in der Schmelze mit HClO4 · H2O als Initiator nimmt die Bruttopolymerisationsgeschwindigkeit exponentiell mit steigender Wasserkonzentration ab; gleichzeitig nimmt die Lange der Induktionszeit entsprechend zu. Die Retardierung durch Wasser wird auf eine Hydratation aktiver Zentren zuruckgefuhrt. Wasser ist ein wirkungsvoller Polymerisationsubertrager; seine relative Ubertragungskonstante betragt bei 25°C in Methylenchlorid ca. 2,6. Jedoch werden die Verhaltnisse durch die Bildung von Methylenglykol aus Wasser und Formaldehyd kompliziert. In polymerization of trioxane in the melt at 70°C. with HClO4 · H2O as initiator the rate of polymerization dec…

Influence of Acidic Support in Metallocene Catalysts for Ethylene Polymerization

2001

Abstract We studied a ZSM-5 zeolite as metallocene support for ethylene polymerization. We transformed the Na-ZSM-5 into H-ZSM-5. After the cation exchange, the zeolite was calcined at three different temperatures. Characterization of the material indicated that by means of the calcination procedure it is possible to produce dealuminization with an increase in extraframework aluminum (EFAL). We prepared zirconocene-supported catalysts on zeolitic supports using two preparation methods. The higher activity was observed with the zirconocene supported on ZSM-5 pretreated at 900°C. We think that the dealuminization process generates an increase in EFAL. This EFAL is responsible for the higher a…