Synthèse du tétraéthoxycarbonyl‐1,1,6,6‐cyclodécadiyne‐3,8

Etournaud, Alain; Wyler, Hugo

doi:10.1002/hlca.19730560208

Cited by 14 publications

(3 citation statements)

References 10 publications

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“…The same authors attempted to prepare the lower homologue 1,6-cyclodecadiyne 2 (n = 3) 'in the h@e that in this compound the two acdtylenic fumtions would be forced into one anothev's electronic environment and would perhafis +assess some cyclobutadiene-like character.' Unlike its higher homologue, however, the precursor dimethyl-5-decynedioate failed to undergo acyloin ring closure and it is only recently that substituted derivatives of 2 (n = 3) have been obtained by alternative routes [5] [6]. Although the heterocyclic analogue 4 (X = 0) has been synthesized by Lespieau [7] as early as 1929 this claim was not generally accepted until 1960 when Sondheimer eta2.…”

Section: Synthesized In 1956 Bymentioning

confidence: 99%

1,5‐Cyclooctadiyne. Preparation and Reactivity

Kloster‐Jensen

Wirz

1975

Helvetica Chimica Acta

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Kfingclbergstrasee 80, CH-4056 Basel. Switzcrlmd (20. XI. 74) Summauy. 1,.5-Cyclooctadiyne 1 was isolated in 2 pcrcent yield from polymerized butatrieno 5. Other oligomcrs of 5 wcre dctected in the reaction mixture by combined GLC./MS. analysis but have not been identified. Diets-Aldev adducts of I with two equivalents of 1,J-butadiene and of 2,3-dimethyI-l.J-butarli~ne have bcan preparcd. In the prescnce of strong base 1 isomorizcd to cyclooctatctraenc. 5 was rcformcd by photolysis of 1. Attcmpts to preparc transition mctal complexes of 1 failed. Effrxts of ring strain and of transannular interaction on the rcactivity of 1 arc discusscd. The dirnerization of 5 to 1 is predicted to be strongly cxothcrmic.The synthesis of medium-sized cyclic alkynes [l] and the investigation of their chemical reactivity as a function of geometric ring strain have been the object of considerable effort during the past twenty years. The smallest unsubstituted cycloalkyne yet isolated is cyclooctyne which was first prepared by Bloquist in 1953 [2], Evidence for the intermediate existence of the lower homologues cycloheptyne, .-hexyne, and -pentyne is limited to trapping and self-trapping reactions [3aJ. ' 1 2 3 4 ---1) Permanent addrcss:

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Section: Synthesized In 1956 Bymentioning

confidence: 99%

1,5‐Cyclooctadiyne. Preparation and Reactivity

Kloster‐Jensen

Wirz

1975

Helvetica Chimica Acta

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“…4 Probably the first functionalized 1,6-cyclodecadiyne was tetraester 3 (Scheme 1) reported by Etournaud and Wyler. 5 The synthesis of 3 was achieved by reaction of 1,4-dihalo-2-butyne with diethyl malonate in presence of a strong base. 5…”

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confidence: 99%

“…5 The synthesis of 3 was achieved by reaction of 1,4-dihalo-2-butyne with diethyl malonate in presence of a strong base. 5…”

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confidence: 99%

Synthesis and Properties of 1,6-Difunctionalized Cyclodeca-3,8-diynes

Chellappan¹,

Haberhauer²,

Feuerbacher³

et al. 2003

Synthesis

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The reaction of tert-butyl acetate (6) with 1,4-dibromobut-2-yne (1) in the presence of LDA yielded 1,6-di(tert-butyl)cyclodeca-3,8-diyne-1,6-dicarboxylate (8). The 1,6-di(tertbutyl) groups of 8 were transferred to bis(hydroxymethyl) (5), bis(bromomethyl) (13), bis(cyanomethyl) (14), dicarbaldehyde (15) and bis(methoxyvinyl) (16) groups. In case of 13 the two diastereomers [cis(a,e), trans(a,a)] were separated . From 13(a,e) and 14(a,a) we were able to obtain detailed structural parameters by means of X-ray crystallography. By means of temperature dependent NMR spectroscopy of 14(a,a) we estimated the activation energy for the chair-boat conversion to be 10.5 kcal/mol.

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