A 1% crosslinked divinylbenzene-styrene copolymer, incorporating benzyl acrylate groups, reacted in normal Diels–Alder reactions with E-1-phenyl-1,3-butadiene or methyl E-2,4-pentadienoate to give their respective polymer-bound benzyl cyclohexenecarboxylates. Polymer-bound benzyl propiolate and polymer-bound benzyl phenylpropiolate reacted with benzonitrile oxide in a typical 1,3-dipolar addition reaction to give their respective polymer-bound isoxazoles. Cleavage of the polymer-bound Diels–Alder adducts and the polymer-bound 1,3-dipolar addition adduct derived from polymer-bound benzyl propiolate gave mixtures of ortho and meta regiomers similar to those produced in analogous reactions in solution. Cleavage of the polymer-bound 1,3-dipolar addition adduct, derived from polymer-bound benzyl phenylpropiolate, followed by esterification, gave a solitary adduct, 4-carbomethoxy-3,5-diphenylisoxazole, but an analogous solution 1,3-dipolar addition yielded a 1:1 ratio of the two possible regiomers.
The uracil analog, 4fluoro.2.pyridone was synthesized by ether cleavage of 4-fluoro-2-methoxypyridine with trimethylsilyl iodide. Improved procedures for the preparatiore of 2-methoxypyridine lV-oxide hydrochloride and 2-methoxy4.nitropyridine y'foxide are described. [6] have been described, the desired ,lfluoro-2-pyridone (l) was unknown. Since it was well documented that 4.fluoropyridine was an unstable elusive compound [7,18], there was concern that the related 4-fluoro-2-pyridone (l) would be difficult to prepare. Although some care must be exercised in the isolation of I (see Experimental), compound I was prepared using sone of the methods related to those of Nesnow and Heidelberger [4]
A 1% crosslinked divinylbenzene–styrene copolymer, incorporating benzyl alcohol groups, was used to monoblock the symmetrical diacid chlorides, ClOC(CH2)nCOCl (where n = 4 and 8). Further reaction of the polymer-bound monoester monoacid chloride with phenylmanganese iodide or butylmanganese iodide gave their respective polymer-bound tertiary hydroxyesters. Subsequent base cleavage and esterification yielded methyl 6-hydroxy-6, 6-diphenylhexanoate, methyl 10-hydroxy-10,10-diphenyldecanoate, methyl 6-butyl-6-hydroxydecanoate, and methyl 10-butyl-10-hydroxytetradecanoate and some recovered dimethyl alkanoates. The reactions of some polymer-bound monoester monoacid chlorides with phenylcadmium chloride were also studied.
Reaktion der aus den Komponenten (I) und (II) erhältlichen polymeren Spezies (III) mit den Dienen (IV) gibt die polymergebundenen Diels‐Alder‐Addukte (V), deren Spaltung und nachfolgende Veresterung Gemische der Isomeren (VIa)+(VIIa) bzw. (VIb)+(VIIb) (jeweils cis‐trans‐Gemisch) liefern.
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