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

  • Samuel Barnett Schryver
Date:
[1899.]
Catalogue details

Licence: Public Domain Mark

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

    4/14 page 662
    The reaction is also applicable to substituted phenols, but of these there are two classes at present known, which will not react with anhydrides in the way just described. (a) The Ortho- and Para-nitrophenols.—Whereas metanitrophenol acts on camphoric anhydride with ease, the ortho-and para-derivatives do not react with it, even when the mixture is heated to 180°. Several instances have been pointed out recently in which the meta-compound acts quite differently from both the ortho- and para- derivatives. Tobry de Bruyn (Rec. Trav. Chern., 1894, 13, 101) has shown that whereas ortho- and para-dinitrobenzene are readily con¬ verted into ethoxynitrobenzenes by the action of alcohol, the meta¬ compound does not react with alcoholic ammonia, even at 250°. Menschutkin {Per., 1897, 30, 2968) shows further that meta- nitrobromobenzene will not react with dipropylamine, although both the ortho- and para-derivatives form condensation products with it with relative ease. On the other hand, metatoluidine acts on allylic bromide more readily than either the ortho- or para-compound, the relative rates of reaction being 54 for the ortho-, 445 for the meta-, and 96 for the para-derivative. It will be noted that in the two cases where a metanitro-compound does not react, the strongly negative nitro-group causes the other substituted group or element to resist the action of a basic substance (alcoholic ammonia or propylamine). The converse is observed, however, in the action of nitrophenols on anhydrides, and whilst the nitro-group protects the hydroxyl radicle in the ortho- or para- position, metanitrophenol readily reacts with a substance of acidic character. (b) The Diortho-substituted Phenols.—V. Meyer and his pupils have shown that substituted benzoic acids, with the two substituent groups in the ortho-position relatively to the carboxylic group, are incapable of forming alkyl salts when treated with an alcohol and hydrochloric acid(V. Meyer and Sudborough, Per., 1894, 27, 510, 512, 1580, 3146); benzamides derived from such acids, moreover, appear to be hydrolysed with very great difficulty (Sudborough, Trans., 1895, 65, 603). The sodium salts of diortho-substituted phenols will not condense with anhydrides. This law has been confirmed by an investigation of the reactions of the following bromophenols with camphoric anhydride : OH OH OH OH /\ /^Br Bi’j/^jBr Br/\: x/1 \/ I 1 Br Br Br 9
    digitised image 1
    digitised image 2
    digitised image 3