Preparation of acid phenylic salts of dibasic acids / by S.B. Schryver.

  • Schryver, S. B. (Samuel Barnett), 1869-1929
Date:
[1899.]
Catalogue details

Licence: Public Domain Mark

Credit: Preparation of acid phenylic salts of dibasic acids / by S.B. Schryver. Source: Wellcome Collection.

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    as it was observed that, whereas the sodium salt of the first two com¬ pounds readily underwent condensation, yielding the well crystallised bromophenyl hydrogen camphorates on acidification, the other two bromophenols did not react even at 180°. The analogy between these facts and those observed by Y. Meyer and his pupils on the etherification of substituted benzoic acids is certainly striking. The general law, however, has only been tested by the xeactions of the bromo-substitution products, as pressure of other voik has prevented me from following this subject further. It must therefore be left an open question whether the non-reactivity of the diortho-substituted products is to be ascribed to the stereochemical influence of the substituent groups (Y. Meyer), or to the proximity of the hydroxyl radicle to two other groups of strongly negative charac¬ ter ; in other words, whether it is due to a dynamic or a static cause. In the action of camphoric anhydride on sodium derivatives of phenols, only one acid phenylic salt was obtained in each case, except in that of metanitrophenyl camphorate, which was formed in very small quantity; the crystalline compounds seemed homogeneous, and melted sharply, frequent recrystallisation failing to alter the melting point to any appreciable extent. No mixtures corresponding to the alio- or ortho-monomethylic salts were obtained (Braunschweig, Per., 1692, 25, 1806; Walker, Trans., 1892, 41, 1089). feeveial of the products described in the following work may find applications for therapeutic purposes. Experimental. I. Action oj Anhydrides on the Sodium Derivatives of simple Phenols, or Ethers of polyhydric Phenols. Phenyl Hydrogen Camphorate, COOH- C8HU-COO-C6H5.—Sodium, in wii e oi small pieces, was added to a molecular proportion of pure phenol dissolved in ten times its weight of xylene, and the mixture warmed to about 90J; the sodium dissolved, and the sodium phenate which is formed separated as a white powder. As soon as this action was com¬ pleted, a molecular equivalent of camphoric anhydride was added to the solution while still warm, and the mixture vigorously shaken ; the sodium phenate dissolved almost immediately, and after a short time sodium phenyl camphorate separated in a gelatinous form. The mixture was vigorously shaken with water, equal in volume to that of the xylene, to dissolve the sodium salt, and on acidifying, phenyl hydrogen camphorate separated as an oil. This was taken up with ether, the ethereal solution dried over calcium chloride, and after distilling off the ether, the residue was left in a vacuum for a few days, when the light yellow oil commenced to solidify, forming hard