The Chemistry of the Aminochromes: Part V. Rearrangements in the Presence of Sodium Hydroxide and Zinc Acetate

Heacock, R. A.; Mattok, G. L.

doi:10.1139/v63-018

Cited by 21 publications

(7 citation statements)

References 4 publications

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“…Earlier investigations on ADR photolysis (λ=254 nm) reported the formation of aminochrome as a main product (16, 24). It was now of interest to determine the products from ADR transients, resulting from the electron emission process.…”

Section: Resultsmentioning

confidence: 99%

Adrenaline: communication by electron emission. Effect of concentration and temperature. Product analysis

Getoff

Huber²,

Hartmann³

et al. 2010

Hormone Molecular Biology and Clinical Investigation

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Section: Resultsmentioning

confidence: 99%

Adrenaline: communication by electron emission. Effect of concentration and temperature. Product analysis

Getoff

Huber²,

Hartmann³

et al. 2010

Hormone Molecular Biology and Clinical Investigation

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“…refs. 14,15,16). This shift of the visible absorption maxiina towards longer wavelengths appears to be associated with 7-substitution.…”

mentioning

confidence: 84%

The Chemistry of the Aminochromes. Part Viii: The Preparation and Properties of 4- And 7-Methyladrenochrome

Heacock¹,

Hutzinger²

1965

Can. J. Chem.

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Two new catecholamines, 2-and 5-methyladrenaline, have been prepared from 3-methylcatechol and they gave 4-and 7-methyladrenochrome, respectively, on oxidation. 7-Iodo-4-methyladrenochrome was obtained on oxidation of 2-methyladrenaline with potassium iodate; however, an iodoaminochrorne could not be obtained in a similar manner from 5-methyladrenaline. T h e expected 5,6-dihydroxyindole derivatives were obtained on reduction of these aminochromes.I t has been known for many years that the oxidation of adrenaline with potassium iodate leads to the forination of deep-violet products (1, 2). The compound responsible for the violet color was first isolated in 1937 by Richter and Blaschko who described it as 3-hydroxy-2-iodo-l-methylindoline-5,6-quo (i.e. 2-iodoadrenochrome) (3). However, it has recently been shown that iodination actually occurs in the 7-position of the adrenochrome nucleus and it was further demonstrated that iodinatioil (and bromination) invariably occurs in the 7-position and not the 2-position in the aminochrome lnolecule (4).As part of a research prograin into the chemistry of the aminochromes, that is being carried out in these laboratories, it was decided to prepare 2-and 5-inethyladrenaline (I and I1 respectively) and t o investigate the effects of the methyl substitution of the aromatic ring on the oxidation of these hitherto unknown catecholamines with several different oxidizing agents.I t was possible t o prepare I and I1 by procedures similar to that originally described by Stolz for the preparation of adrenaline (5). w-Chloro-3,4-dihydroxy-2-methylacetophenone (111) was prepared froin 3-inethylcatechol (IV) by a Friedel-Crafts condensation with chloracetyl chloride in the presence of aluminium chloride in carbon disulfide solution. Methylation of the phenolic hydroxy groups of I11 gave w-chloro-3,4-dimethoxy-2-methylacetophenone (V), a compound that had previously been described in the literature (6), proving that the chloroacetyl residue had entered the aromatic ring of IV in the position ortho to the inethyl group. The n.m.r. spectrum of I11 in hexadeuteroacetone showed two well separated doublets centered a t 6 7.38 and 6 6.92 with a coupling constant of ca. 8.5 c.p.s., indicating the presence of two ortho aromatic hydrogens in the molecule and confirming the position of the chloroacetyl residue. w-NIethylamino-3,4-dihydroxy-2-methylacetophenone (VI) was prepared by treating I11 with methanolic methylainine a t room temperature (cf. ref. 7). Treatment of I11 with sodium iodide in acetone gave 3,4-dihydroxy-w-iodo-2-lnethylacetophenone (cf. ref. 6). Preliminary experiments indicated that there was no advantage in using the w-iodo derivative t o prepare VI. 2-Methyladrenaline (I) was obtained in good yield by catalytic hydrogenation of VI. The hydrochloride of I was hygroscopic, but the acid oxalate salt of I was not and was readily purified by recrystallization from aqueous ethanol.

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“…The rates of decoinposition of adrenochrome in the presence of inorganic cornpounds were followed by the method described by Heacock and Mattol; (10). When no catalyst was present in the solution the reaction inixtures were inaintained a t constant temperature in a thermostatted water bath.…”

Section: Methodsmentioning

confidence: 99%

“…in solution. Recently the mechanism of the rearrangement of the aminochromes in water, aqueous alkali, and aqueous zinc acetate has been studied (10).…”

Section: Introductionmentioning

confidence: 99%

The Stability of Adrenochrome and Its Solutions

Heacock

Mattok

Wilson

1963

Can. J. Biochem. Physiol.

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The Chemistry of the Aminochromes: Part V. Rearrangements in the Presence of Sodium Hydroxide and Zinc Acetate

Cited by 21 publications

References 4 publications

Adrenaline: communication by electron emission. Effect of concentration and temperature. Product analysis

Adrenaline: communication by electron emission. Effect of concentration and temperature. Product analysis

The Chemistry of the Aminochromes. Part Viii: The Preparation and Properties of 4- And 7-Methyladrenochrome

The Stability of Adrenochrome and Its Solutions

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