Cyclobutane Derivatives. II. The Thermal Decomposition of trans-1,2-Cyclobutane- bis-(trimethylammonium) Hydroxide

Buchman, Edwin R.; Schlatter, Maurice J.; Reims, Alf O.

doi:10.1021/ja01263a049

Cited by 17 publications

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“…A similar hydrolysis has been proposed byBuchman, Schlatter, and Reims(1) to explain the formation of cyclobutanone and dimethylamine in the thermal decomposition of trans-l,2-cyclobutane-bis-(trimethylammonium)hydroxide; this decomposition presumably proceeds stepwise, over an intermediate vinylic (or allylic) trimethylammonium base 4. Quite recently, with reference to application of the decomposition of an allylic quaternary ammonium base to the synthesis of vitamin A, Milas (2) has written that "trimethylallylammonium hydroxide gives, on heating, chiefly trimethyl amine and allyl alcohol" without any further substantiation of this statement 4.…”

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confidence: 68%

“…The material (ca. 1 ml., see above) collected in the Dry-Ice trap was allowed to warm to room temperature and thus (except for about 0.1 ml. of higher-boiling material) distilled through a short tube of Drierite into an ampule cooled in Dry-Ice, yield 0.67 g. (34%)7 of a mixture of methylacetylene and aliene (see below); the action of Nessler's reagent on this material, following the directions of Johnson and McEwen (18), gave 1.03 g. (44%) of crude mercuric methylacetylide; continuous extraction with acetone gave white flaky crystals, m.p.…”

Section: Experimental Partmentioning

confidence: 99%

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The Thermal Decomposition of Allyltrimethyl-Ammonium Hydroxide

Howton¹

1949

J. Org. Chem.

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Current studies in this Laboratory involve the thermal decomposition of certain allylic trimethylammonium hydroxides. The observation that quite appreciable amounts of dimethylamine and saturated carbonylic compounds are formed in these reactions has led to the belief that these quaternary bases rearrange to some extent during the pyrolysis, giving vinylic trimethylammonium bases. Although it is conceivable that the carbonylic products might be formed by the rearrangement of allylic alcohols derived from the unrearranged quaternary bases, the only readily understood mechanism by which dimethylamine could be formed involves the hydrolysis of a vinyldimethylamine, formed by an Sn2 attack by hydroxyl ion upon a methyl group of the vinyltrimethylammonium ion. The products of such a reaction would be methanol and a vinyldimethylamine, which would be hydrolyzed (in the dilute acid commonly used to absorb the bases formed in Hofmann degradations) to dimethylamine and a saturated carbonylic compound.1 2 A thorough examination of the products formed in the thermal decomposition of the simplest allylic trimethylammonium hydroxide (I) was considered worth while to substantiate these findings and postulates.The pyrolysis of I has not been studied for over half a century,3 and then only cursorily. In an obscure publication which appeared in 1886 and has since been overlooked or discredited, Bono (3) heated allyltrimethylammonium iodide with potassium hydroxide and obtained an aldehyde, CeHioO, whose boiling point, 130-135°( as he pointed out) corresponded to that of a-methyI-/3-ethylacrolein (IV), the only aldehyde of that formula known at that time; since our findings (see below) substantiate Bono's identification of this product,4 the question mark appearing in Beilstein's account (5) of his work should be deleted. A short time

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supporting

confidence: 68%

Section: Experimental Partmentioning

confidence: 99%

The Thermal Decomposition of Allyltrimethyl-Ammonium Hydroxide

Howton¹

1949

J. Org. Chem.

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Olefins from Amines: TheHofmann Elimination Reaction and Amine Oxide Pyrolysis

Cope

Trumbull

2011

Organic Reactions

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The conversion of an amine to an olefin by elimination of the nitrogen atom and an adjoining hydrogen atom is a useful procedure for degradation and synthesis. The Hofmann exhaustive methylation method has been used most often to bring about change, but other methods as the thermal decomposition of amine oxides and the pyrolysis of amine phosphates or acetyl or benzoyl derivative have often been employed to advantage. This chapter reviews the Hofmann elimination because of its extensive history. Alternative methods are considered.

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Kleine Kohlenstoff‐Ringe

Vogel

1960

Angewandte Chemie

147

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Die Fortschritte der präparativen Methoden haben in den letzten Jahren zu einer stürmischen Entwicklung des bisher nur wenig erschlossenen Gebietes der kleinen Kohlenstoff‐Ring (3 und 4 Glieder) geführt. Im Zuge der jüngsten Forschungen wurden zahlreiche Ringsysteme bekannt, deren Existenz man früher auf Grund ihrer Spannung nicht für möglich gehalten hätte. Valenzisomerisierungen von zum Teil leicht zugänglichen mono‐, di‐ und tricyclischen Derivaten des Cyclopropans und Cyclobutans eröffneten neue Wege zum 7‐ und 8‐Ring. Das seit den klassischen Untersuchungen von Willstätter jahrzehntelang nicht bearbeitete Cyclobutadien‐Problem konnte durch wesentliche experimentelle und theoretische Beiträge einer Lösung näher gebracht werden. Eine weitere Bereicherung erlebte die Chemie der kleinen Ringe durch die Auffindung neuartiger Cyclopropan‐ und Cyclobutan‐Verbindungen in der Natur

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Cyclobutane Derivatives. II. The Thermal Decomposition of trans-1,2-Cyclobutane- bis-(trimethylammonium) Hydroxide

Cited by 17 publications

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The Thermal Decomposition of Allyltrimethyl-Ammonium Hydroxide

The Thermal Decomposition of Allyltrimethyl-Ammonium Hydroxide

Olefins from Amines: TheHofmann Elimination Reaction and Amine Oxide Pyrolysis

Kleine Kohlenstoff‐Ringe

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