Über Ringschlußreaktionen im Anschluß an die Allenumlagerung von 1‐Methoxy‐1.1.5.5‐tetraaryl‐pentin‐(2)‐onen‐(4) mit anorganischen Säurehalogeniden

Acetylenketone 1 und CH-acide Verbindungen von der Art des Dibenzylketons reagieren in Gegenwart von K-tert.-butglat zu substituierten Phenolen 4. 2.3.5.6-Tetrasubstituierte Phenole werden mit CrO,/Eisessig je nach Substitution zu Benzochinonen l l a -f bzw. zu Fluorenchinonen 9 und 10 oxydiert. In HBr/Eisessig reagieren Phenole vom Typ 4a bzw. 4f zu Fluorenolen, wic: 12, bzw. zu Phthalanen, wie 13. Cyclisation Reactions of Alkynones with Double CH-Acid Compounds to PhenolsAlkynones 1 and CH-acid compounds like dibenzyl ketone react to substituted phenols 4 in the presence of K-tert-butylate. Depending on the substituents, 2,3,5,6-tetrasubstituted phenols are oxidized by Cr03/acetic acid to benzoquinones l l a -f or fluorene quinones 9 and 10. In a solution of HBr/acetic acid phenols of the type of 4a or 4f form fluorenols like 12 or phthalanes like 13. Darstellung von AcetylenketonenAcetylen-Grignard-Verbindungen reagieren mit Aldehyden zu sekundaren Alkinolen 2). Diese werden durch Cr03-Oxydation in Acetylenketone uberfuhrt. Nach dieser Methode lassen sich die Acetylenketone l a -d in guten Ausbeuten darstellen.

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1‐Halo‐1‐acceptor‐/1,1‐diacceptor‐substituted Allenes, 9. Functionalized Allenes, Haloallenes, and Bisallenes via [2,3]/[3,3]‐Sigmatropic Rearrangements and Their Reactivity

Saalfrank¹,

Welch²,

Haubner³

et al. 1996

Liebigs Ann./Recl.

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Reaction of carbonyl compounds 1 with trimethylsilylacetylene 2 leads to the alkynols 3, which are excellent precursors of acceptor-substituted allenes. Compound 3 reacts with carbamoyl chloride 4, diethyl chlorophosphate 6, or hypohalite 8 to give the substituted alkynols 5, 7, 9. Reaction of 9 with sulfinyl chloride 10 leads to the sulfinic esters 11, which on heating undergo a [2,3]-sigmatropic shift to yield the halosulfonyl allenes 12. In the same manner the reaction of 7 and 9 with chlorophosphanes 13 or sulfenyl chlorides 15 gives rise to the generation of the phosphoryl allenes 14 and the haloallenyl sulfoxides 16, respectively. Alkynyl ketene acetal intermediates 18 are formed by starting from the alkynols 9 and orthoesters 17. Spontaneous [3,3]-sigmatropic rearrangement of 18 gives the haloallenyl esters 19. Reaction of alkynols 5 with sulfur dichloride leads to the alkynylsulfinyl esters 20, which on heating rearrange to the bisallenyl sulfones 21. Pyrolysis of 21 yields the thiophene 1,l-dioxides 22. Bisphosphorylbisallene 24 is synthesized from hexadiyndiol23 by reaction with chlorodiethoxyphosphite. Halophosphoryl allenes 14 react with bromine to yield the oxaphospholenes 25 by cyclization and subsequent elimination of ethanol, or oxaphospholenes 26, if no appropriate leaving group is present in the molecule. Sulfonyl-1,3-dienes 27 can be synthesized by reaction of halosulfonylallenes 12 with bromine, followed by elimination of HBr. Haloallenyl ester 19a is converted in a non-generalizable reaction with bromine into the tribromo-3,6-dihydro-2-pyranone 30.During our recent investigations of acceptor-substituted allenes we accomplished the synthesis of allene-1, l-dicar- For the synthesis of the 1-halo-1-sulfonylallenes 12 the halo alkynols 9 are treated with the sulfinyl chlorides 10 in the presence of triethylamine. The primarily formed alkynylsulfinyl esters 11 are surprisingly stable. Only by heating of 11 in toluene at 80°C is the isomerization to the allenes 12 via [2,3]-sigmatropic rearrangement[l4I achieved quantitatively. Reaction of the alkynols 7 and 9 with chlorophosphanes 13 or sulfenyl chlorides 15 in the presence of triethylamine yields directly the allenylbisphosphonic diethyl ester 14a, the 1-halo-1-phosphorylallenes 14b-m and the 1-halo-allenyl 1-sulfoxides 16, respectively. In the case of 14 and 16, the in situ generated alkynyl derivatives, corresponding to the alkynylsulfinylesters 11, cannot be isolated, but rather undergo spontaneous [2,3]-sigmatropic rearrangement to the observed products 14 and 16.

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Über Ringschlußreaktionen im Anschluß an die Allenumlagerung von 1‐Methoxy‐1.1.5.5‐tetraaryl‐pentin‐(2)‐onen‐(4) mit anorganischen Säurehalogeniden

Cited by 3 publications

References 34 publications

ChemInform Abstract: RINGSCHLUSSRK. IM ANSCHLUSS AN DIE ALLENUMLAGERUNG VON 1‐METHOXY‐1,1,5,5‐TETRAARYL‐PENTIN‐(2)‐ONEN‐(4) MIT ANORGANISCHEN SAEURECHLORIDEN

ChemInform Abstract: RINGSCHLUSSRK. IM ANSCHLUSS AN DIE ALLENUMLAGERUNG VON 1‐METHOXY‐1,1,5,5‐TETRAARYL‐PENTIN‐(2)‐ONEN‐(4) MIT ANORGANISCHEN SAEURECHLORIDEN

Ringschlußreaktionen von Acetylenketonen mit zweifach CH‐aciden Verbindungen zu Phenolen

1‐Halo‐1‐acceptor‐/1,1‐diacceptor‐substituted Allenes, 9. Functionalized Allenes, Haloallenes, and Bisallenes via [2,3]/[3,3]‐Sigmatropic Rearrangements and Their Reactivity

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