Preparation of 1-C<sup>14</sup>-Propene-1 and the Mechanism of Permanganate Oxidation of Propene<sup>1</sup>

Fries, B.A.; Calvin, Melvin

doi:10.1021/ja01186a072

Cited by 15 publications

(1 citation statement)

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“…2), first of all, the designation of the C14 location in XVIII is most probably correct since the conversion of X I to XVIII involved an SN2 type of direct displacement and a double decomposition reaction both of which are not likely to cause isotope position rearrangements. Moreover, XVIII was prepared in a manner analogous to the synthesis of 1z-propyl-3-C~~-trimethyla1nino11ium hydroxide, which has been found to undergo successful thermal decompositioll to propene-1-C14 (16). The randomized C14 distribution in the cyclopentadiene from synthesis No.…”

Section: (Xi ( X V I I ) ( X V L B L ( X V I L L )mentioning

confidence: 99%

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C¹⁴ AS TRACER

Tkachuk¹,

Lee²

1959

Can. J. Chem.

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Starting with formaldehyde-C1" 1,2-dibromocyclopentane-4-C" ( X I ) was synthesized in eight steps. Conversion of X I to cyclopentadiene was accomplished in three different ways, namely: the dehydrobromination of X I with quinoline a t 195-198' C, the preparation of 1,2-bis-(trimethylammonium)-cyclopentane-4-14 hydroxide from X I followed by thermal decomposition, and the conversion of X I to 3,5-dibromocyclopentene followed by reaction of the latter with magnesium in d r y ether. Degradations of the samples of cyclopentadiene obtained by these three synthetic routes showed a completely randomized distribution of the Cld activity, with 20y0 of the total activity on each of the five carbon positions. These results led t o the conclusion that these preparations of cyclopentadieile very likely involved ionization to the cyclopentadienyl anion. T h e randomized distribution of C" in the resulting products thus furnishes a strong indication that all five carbon positions in the cyclopentadienyl anion are equivalent. INTRODUCTIONT h e acidity of cyclopentadiene was first recognized i11 1900 by Thiele (I), and its potassium salt was prepared in 1901 (2). This salt is stable, though very reactive. The reason for the stability of salts containing the cyclopentadienyl anion has been given asearly as 1928, by Goss and Ingold (3), and is that this ion has six (n) electrons, distributed over the entire five-membered ring, thus constituting a stable aromatic system similar to benzene. T h e resonance energy of this ion has been calculated to be about 42 kcal per mole (4).Salts of cyclopentadiene with organic cations are also known. Pyridi~lium cyclopentadienylide has been described by Lloyd and Sneezum (5) and by Kosower and Ramsey (6). Triphenylphosphonium cyclopentadienylide has also been reported (7).From theoretical considerations and physical chemical measurements, a number of workers (4,(8)(9)(10)(11)(12) have predicted that the ~legative charge on the cyclopentadiellyl anion will not be localized on a partic~ilar carboll atom but will be distributed over theion as a whole, as depicted by I. In the present study, attempts were made to obtain, by the tracer technique, some direct experimental evidence ill support of these theoretical predictions.If it were possible to synthesize cyclopentadiene-5-C14 (11), conversion of this conlpound to its potassi~~m salt followed by regeneration should yield a cyclopentadiene in which the C14 distribution could provide definitive evidence for the struct~ire of the cyclopentadienyl anion. Should the anion have the symmetrical electronic structure I, on 'Manuscript

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Section: (Xi ( X V I I ) ( X V L B L ( X V I L L )mentioning

confidence: 99%

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C¹⁴ AS TRACER

Tkachuk¹,

Lee²

1959

Can. J. Chem.

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Small‐scale degradation of carbon‐14 labelled carboxyl acids. III. Degradation of acetic acid−¹⁴C

Numrich

Nystrom

1971

J. Labelled Cpd. Radiopharm.

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Oxidation of propene‐1‐¹⁴C to acrolein on copper catalysts

Sixma

Duynstee

Hennekens

1963

Recl. Trav. Chim. Pays‐Bas

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Propene‐1‐14C was partially oxidised with air to acrolein on a copper catalyst. The acrolein formed was degraded: equal amounts of radioactivity were found on carbon atoms 1 and 3, while essentially no radioactivity was found on the middle carbon atom (2). The “unreacted” propene was also degraded: a major part of the radioactivity was still on carbon atom 1, while a small part (10‐20%) was on carbon atom 3; no radioactivity was found on the middle carbon atom (2). These facts indicate that the oxidation of propene to acrolein on a copper catalyst takes place via a symmetrical intermediate. Partial isomerisation of unreacted propene also occurred when copper shavings were used as a catalyst. When D2O was present during the reaction, the unreacted propene was monodeuterated to only a very small extent (∼2%).

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Preparation of 1-C¹⁴-Propene-1 and the Mechanism of Permanganate Oxidation of Propene¹

Abstract: IrLf o r a a t i o n i~i v i~ ior, and r.l;.cnrd , d tilere. UNIVERSI TY OF CALIFORNIA RADI AT1 ON LAB ORATORY Contract No.. W-7405-Eng .-48

Cited by 15 publications

References 4 publications

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C¹⁴ AS TRACER

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C¹⁴ AS TRACER

Small‐scale degradation of carbon‐14 labelled carboxyl acids. III. Degradation of acetic acid−¹⁴C

Oxidation of propene‐1‐¹⁴C to acrolein on copper catalysts

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Preparation of 1-C14-Propene-1 and the Mechanism of Permanganate Oxidation of Propene1

Abstract: IrLf o r a a t i o n i~i v i~ ior, and r.l;.cnrd , d tilere. UNIVERSI TY OF CALIFORNIA RADI AT1 ON LAB ORATORY Contract No.. W-7405-Eng .-48

Cited by 15 publications

References 4 publications

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C14 AS TRACER

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C14 AS TRACER

Small‐scale degradation of carbon‐14 labelled carboxyl acids. III. Degradation of acetic acid−14C

Oxidation of propene‐1‐14C to acrolein on copper catalysts

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Preparation of 1-C¹⁴-Propene-1 and the Mechanism of Permanganate Oxidation of Propene¹

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C¹⁴ AS TRACER

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C¹⁴ AS TRACER

Small‐scale degradation of carbon‐14 labelled carboxyl acids. III. Degradation of acetic acid−¹⁴C

Oxidation of propene‐1‐¹⁴C to acrolein on copper catalysts