1986
DOI: 10.1002/cber.19861190606
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Cyclophane, 26. Über die Funktionalisierung der Ethanobrücken von [2.2]Paracyclophan

Abstract: An improved procedure for the syntheses of [2.2]paracyclophan-l-ene (4) is described. Addition of halogen to this olefin, subsequent dehydrohalogenation, and again addition and elimination provides a wide range of bridge-halogenated cyclophanes. The derivatives 6 b and 3 were converted into the nitriles 9 and 12 by reaction with copper(1) cyanide in Nmethylpyrrolidone. Subsequent reduction with DIBAH leads to the aldehydes 10 and 13, respectively, which may be converted into the methylcyclophanes 11 and 14 by … Show more

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Cited by 20 publications
(8 citation statements)
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“…Moreover, this first fraction has a characteristic 1 H NMR spectrum, that coincides with the signals marked with • in Figure 1 b. Comparison with literature NMR data supported the intuitive first interpretation that a [2.2]paracyclophane was obtained 18. The 1 H and 13 C NMR spectra of most of the later chromatographic fractions pointed towards these also being cyclodimerized products.…”
Section: Methodssupporting
confidence: 75%
“…Moreover, this first fraction has a characteristic 1 H NMR spectrum, that coincides with the signals marked with • in Figure 1 b. Comparison with literature NMR data supported the intuitive first interpretation that a [2.2]paracyclophane was obtained 18. The 1 H and 13 C NMR spectra of most of the later chromatographic fractions pointed towards these also being cyclodimerized products.…”
Section: Methodssupporting
confidence: 75%
“…Reaction of [2.2]paracyclophane 3 with NBS gave the corresponding product 1‐bromo[2.2]paracyclophane 5 triggered by azodiisobutyronitrile (AIBN). Subsequent dehydrobromination using potassium tert ‐butoxide/DMSO resulted in [2.2]paracyclophan‐1‐ene 6 in 62% yield 16. Then treatment of olefin 6 with chlorodiphenylphosphine at room temperature in anhydrous THF afforded 1‐diphenylphosphine‐2‐chloro[2.2]paracyclophane 7 in 48% yield.…”
Section: Methodsmentioning
confidence: 99%
“…Im 1 H‐NMR‐Spektrum zeigt diese Fraktion ein charakteristisches Signalmuster, das insbesondere die in Abbildung 1 b mit • gekennzeichneten Signale enthält. Ein Vergleich mit literaturbekannten NMR‐Daten stützte die anfängliche Vermutung, dass es sich bei dem Öl um ein [2.2]Paracyclophan‐Derivat handelte 18. Die 1 H‐ und 13 C‐NMR‐Spektren der nachfolgenden Fraktionen wiesen ebenfalls auf cyclodimerisierte Produkte hin.…”
Section: Methodsunclassified