The action of nitric acid on the ethers of aromatic hydroxyaldehydes / by Arthur H. Salway.

  • Salway, Arthur Henry.
Date:
1909
Catalogue details

Licence: Attribution 4.0 International (CC BY 4.0)

Credit: The action of nitric acid on the ethers of aromatic hydroxyaldehydes / by Arthur H. Salway. Source: Wellcome Collection.

Provider: This material has been provided by The Royal College of Surgeons of England. The original may be consulted at The Royal College of Surgeons of England.

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    CXXX.— The Action of Nitric Acid on the Ethers of Aromatic Hydroxycddehydes. By Arthur Henry Salway. In the coui’se of some experiments on the synthesis of substances allied to cotarnine, the author had occasion to prepare a compound of the formula (I), and an attempt was made to achieve this object by OHj< OMe (I.) (II.) the action of nitric acid on myristicinaldehyde (II). The yield of the desired nitroaldehyde was comparatively small, the principal product of the reaction being a neutral aitro-compound, which did not contain an aldehyde group, and was found to consist of a nitromethoxymethylene- dioxybenzene. The formation of the latter compound from myristicin- aldehyde is evidently due to the elimination of the aldehyde group and the introduction of a nitro-group into the nucleus. It will be seen that the orientation of the nitro-group in this nitro- methoxymethylenedioxybenzene is essential for the correct interpreta- tion of the manner in which the aldehyde group is eliminated. Thus it might be supposed, on the one hand, that the aldehyde group under- goes direct substitution by a nitro-group, in which case'the constitu- tion of the resulting nitro-compound would be represented by formula (III); on the other hand, it is conceivable that the myristicinaldehyde primarily undergoes nitration with the formation of nitromyristicin- aldehyde, which, by oxidation to the corresponding nitrocarboxylic acid and subsequent liberation of carbon dioxide, becomes converted into a nitromethoxymethylenedioxybenzene. In this case the con- stitution of the latter would be represented by (IV) or (Y). The formation of nitromyristicinaldehyde as one of the products of the nitration of myristicinaldehyde lends some degree of probability to the latter view. However, on further oxidising nitromyristicin- aldehyde, the only product was the stable nitromyristicinic .acid, and there was no evidence of the formation of nitromethoxymethylene- dioxybenzene. It appeared, therefore, improbable that this compound owes its formation to the intermediate production of nitromyristicin- aldehyde according to (lY) or (Y), and it was subsequently proved beyond question by the following series of reactions that nitromethoxy- methylenedioxybenzene is produced by the direct substitution of the ftldehyde group according to (III). CH,< o^Ncho 0 NO, OMe Of >CHO oi