Belt-Shaped Molecules by a Repetitive Synthetic StrategyBelt-shaped molecules of the general type 2 containing up to five benzene ring units (cf. 37

Fast-atom bombardment (FAB) and plasma desorption mass spectrometry of high molecular weight addition polymers of 2,2-bis[4-(2,3-epoxypropoxy)phenyl]propane (DGEBA) and aniline show protonated molecular ions of the intact polymer and oligomer molecules. The oligomeric products consist mainly of cyclooligomers. Their formation can be observed during the polymerization reaction. Telechelic prepolymers having epoxide end groups as well as telechelics containing amino end groups were found with lower degree of polymerization in the mass spectra. Side reactions such as ether formation or epoxide polymerization were not observed. Telechelic DGEBA-aniline prepolymers are shown to consist of a series of oligomers as shown by highpressure liquid chromatography (HPLC) analyses. Consequently, the FAB mass spectra of the prepolymers show molecular ions of the different oligomers. Furthermore, under the conditions of the FAB mass spectrometric analysis fragmentation of the prepolymers to iminium fragment ions was observed.

Plasma desorption (PD) mass spectra of high molecular weight addition polymers of 2.2‐bis‐[4‐(2.3‐epoxypropoxy)phenyl]propane (DGEBA) and benzylamine show protonated molecular ions of the intact polymers and oligomer molecules. In the spectrum of a DGEBA/N,N′‐dibenzyl‐5‐oxanonanediamine‐1.9 addition polymer only fragments of the oligomers and a cyclic oligomer are observed. In both polymer spectra there is no indication for side reactions during the addition polymerization such as ether formation. Fast‐atom bombardment (FAB) spectra of telechelic prepolymers having amino end groups show the regular oligomers with increasing degree of polymerization and the expected fragmentation products. Only prepolymers with epoxide end groups contain the regular prepolymers as well as side reaction products which are formed by reactions of the telechelics and DGEBA or by reaction of themselves. © 1996 John Wiley & Sons, Inc.

A New Deltaphane and Ribbon-Shaped CyclophanesThe reaction of the fourfold functionalized [3.3] CH-n-Wechselwirkung eines bandformigen Cyclophans rnit ToluolWie bereits fruher berichtet[l01, laDt sich die Schliisselsubstanz der Synthese giirtelformiger Molekule, das metal meta-Cyclophan 4 (Ausbeute 28%) zusammen rnit dem isomeren ortholmeta-Cyclophan 5 (Ausbeute 24%) durch eine doppelte Cyclisierungsreaktion von 6 rnit zwei Aquivalen-

Anorganische Festkorper, die sich von den Silikaten ableiten und reaktive organische Gruppen auf der Oberflache besitzen, wurden durch Polymerisation der entsprechenden Monomeren [Trichlor]-[3-(4-chlormethylphenyl)propyl]silan @a), [Dichlor]-[4-(4-~hlormethylphenyl)butyl]methylsilan (5 b) und [Chlor]-[4-(4-~hlormethylphenyl)butyl]dimethy~silan (512) auf porosem Glas hergestellt. Die alkylsubstituierten Mane sind nach einem allgemeinen Schema katalytische Addition von w-(4-Chlormethylphenyl)-l-alkenen an substituierte Chlorsilanezuganglich. Die anorganischen Matrizen mit reaktiven Chlorbenzylgruppen an der Oberflache konnen fur die Festphasensynthese nach Merrifield und ini Saulenverfahren verwendet werden, wie mit der Synthese von H-L-Gln-L-Gln-Gly-Gly-L-Tyr-NHz gezeigt wird. Silicone Matrices for Solid-Phase Peptide SynthesesInorganic solids derived from silicates with reactive organic groups on the surfact are prepared by the polymerisation of the corresponding monomers [trichloro]-[3-(4-chloromethylphenyl)propyl]silane (5a), [dichloro]-[4-(4-chlorophenylmethyl)butyl]methy~silane (5 b), and [chlorol-[4-(4-~hlorophenylmethyl)butyl]dimethy1silane (5c) on porous glass. The alkyl-substituted silanes are accessible according to a general schemecatalytic addition of w-(4-chloromethyl-pheny1)-1-alkenes to substituted chlorosilane. The inorganic matrices with reactive chlorobenzyl groups on the surface can be used for Merrifield solid-phase syntheses and also in a column procedure, as is shown for the synthesis of H-L-Gln-L-Gln-Gly-Gly-L-Tyr-NHZ.Einer der bekanntesten Nachteile der Festphasen-Peptidsynthese von Merrijieldl. 2) ist die nicht vollstandige Kupplungsreaktion, die Fehlersequenzen zur Folge hat3.4). Ferner ist es bei ihr technisch schwierig, die Synthese in einer Saule auszufuhren, da die Polystyrolharze in verschiedenen Losungsmitteln unterschiedlich quellen.Urn die von den Harzen verursachten Schwierigkeiten beim Massentransport der Reagenzien und Losungsmittel zu vermeiden, haben Buyer und Mitarbeiter3) Glaskugeln, die mit Harz belegt waren, fur die Synthese in Saulen verwendet. Diese Technik ist spater von Scott und Mitarbeitern 5.6) quantitativ ausgearbeitet worden ; auch sie *) Korrespondenz bitte an diesen Autor richten. * * ) Herrn Prof. Dr. Th. Wieland zum 60. Geburtstag gewidmet.