Effect of Associated Salts on the Polymerization of Butadiene by Organosodium Reagents

Morton, Avery A.; Bolton, Frank H.; Collins, Frances W.; Cluff, E. F.

doi:10.1021/ie50516a035

Cited by 18 publications

(2 citation statements)

References 6 publications

(13 reference statements)

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“…For the reactions described in this paper no proof for a biradical transition state is offered, but for that matter no proof for an ionic state can be given.4 4 After this paper was written, Bryce-Smith, Gold, and Satchell reported in the Journal of the Chemical Society, 2743 (1954), that deuterated benzene and toluene reacted more slowly with an organoalkali metal reagent, ethylpotassium, than did their hydrogen isotopes. Accordingly they judged the rate-determining step to be the removal of a proton or deuteron by the anion and claimed support for a "protophilic" mechanism.…”

Section: Consistency Of Alkoxide Influencementioning

confidence: 99%

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS^{1, 2}

Morton¹,

Claff²,

Collins³

1955

J. Org. Chem.

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IKTRODUCTIONThis work was intended to be a study of the metalation of the benzene nucleus under the directing influence of an alkyl group which couId not itself be metalated, but steric factors probably limit the scope of polar influence. KO ortho metalation occurs. Only one dimetalation, the m,m', can take place because of the hindrance at the two ortho positions and the failure of sodium to attack a position adjacent to another sodium ion on the ring. Nevertheless some excellent demonstrations of the effects of associated salts, which is one of the special aspects of the work in this laboratory, have been achieved.

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Section: Consistency Of Alkoxide Influencementioning

confidence: 99%

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS^{1, 2}

Morton¹,

Claff²,

Collins³

1955

J. Org. Chem.

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“…Benzylsodium, which is second in the list, would not ordinarily be chosen as a metalating agent for olefins and triphenylmethylsodium and fluorenylsodium even less so because of the difference in pK value (7, 8) of the hydrocarbons. The very strong halide salt influence in the three phenylsodium tests is reminiscent of the salt influence in the polymerization of butadiene by phenylsodium (9) and in the Alfin catalysts (10), where metalation seems of less importance than orientation on the surface (11). Diallylsodium was surprisingly inactive for an alkenylsodium type of compound but intramolecular coordination about sodium, as shown in the formula, might account for the reduced isomerizing activity.…”

Section: Table III Isomerization Of Pentene-1 By Various Alkali Metal...mentioning

confidence: 88%

PYROLYSIS OF AMYLSODIUM AND THE ISOMERIZATION OF ALKENES BY ORGANOSODIUM REAGENTS¹

Morton¹,

Lanpher²

1955

J. Org. Chem.

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Previous work (1,2) in this laboratory upon the pyrolysis of amylsodium has shown its instability and the influence of associated salts. In the present work this organosodium compound was pyrolyzed as a dry solid under a vacuum in order to observe if both pentane and pentene were present or (4) if the hydrocarbon were only the alkene, as had been observed in the pyrolysis of butyllithium (3). Pentane proved to be present in large amount. Pentene-1 was found at 90°a nd 75°b ut, surprisingly, irans-pentene-2 was found also, and in increasing amounts as the temperature fell. At 50°this trans isomer was the sole olefin. Pentene-1 might have changed to irans-pentene-2 if it had remained long enough -SUMMARY 1. Decomposition of amylsodium at 90, 75, and 50°under a vacuum yielded progressively less pentene-1. At the lowest temperature the olefin was entirely trans-pentene-2.2. Pentenylsodium caused the isomerization of hydrocarbons with terminal vinyl groups and the process was exceedingly rapid with any n-alkene-l tested.3. The isomerization of pentene-1 to fmns-pentene-2 took place in decreasing velocity as pentenyl-, benzyl-, octenyl-, amyl-, phenyl-, triphenylmethyl-, and allyl-(alfin) sodium compounds were used.4. With phenylsodium the isomerizing activity decreased as the sodium compound was made from chloro-, bromo-, and iodo-benzene.Cambridge 39, Mass.

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Über die stereospezifische polymerisation von styrol mit natriumorganischen verbindungen

1958

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Es wird über die Herstellung von kristallisierbaren Polystyrolen durch Polymerisation von Styrol mit natriumorganischen Verbindungen bei niedrigen Temperaturen berichtet. Anteile der Polymeren sind röntgenkristallin und haben Schmelzpunkte von über 200°C. Dieser kristallisierbare Anteil nimmt mit fallender Polymerisationstemperatur zu. Bei konstanter Polymerisationtemperatur fallen die Viskositätszahlen der Polymeren mit steigender Katalysatorkonzentration.

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Effect of Associated Salts on the Polymerization of Butadiene by Organosodium Reagents

Cited by 18 publications

References 6 publications

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS^{1, 2}

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS^{1, 2}

PYROLYSIS OF AMYLSODIUM AND THE ISOMERIZATION OF ALKENES BY ORGANOSODIUM REAGENTS¹

Über die stereospezifische polymerisation von styrol mit natriumorganischen verbindungen

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Effect of Associated Salts on the Polymerization of Butadiene by Organosodium Reagents

Cited by 18 publications

References 6 publications

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS1, 2

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS1, 2

PYROLYSIS OF AMYLSODIUM AND THE ISOMERIZATION OF ALKENES BY ORGANOSODIUM REAGENTS1

Über die stereospezifische polymerisation von styrol mit natriumorganischen verbindungen

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CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS^{1, 2}

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS^{1, 2}

PYROLYSIS OF AMYLSODIUM AND THE ISOMERIZATION OF ALKENES BY ORGANOSODIUM REAGENTS¹