O-Benzoic Sulphinide (Saccharin) Ferridehemoglobin.

Abstract

In discussing the reactions of nitrite with blood pigment, Gamgee 1 claimed priority on the discovery of the class of ferrihemoglobin derivatives typified by the cyanmethemoglobin of Kobert. 2 Smith and Wolf 3 discovered the azide and Haurewitz, 4 the fluoride derivatives.

On the basis of its potentiometric behavior, Barnard 5 characterized alkaline ferrihemoglobin as the hydroxide of this class and predicted the ability of ferrihemoglobin to form polar valent compounds with many anions. Keilin 6 described the hydrosulfide of ferrihemoglobin and in 1937, Barnard 7 designated the class of derivatives as “hemo-ferrides” to emphasize their binary nature, i.e., they were salts of hydro-acids, exclusively. On the basis of the demonstration of the nitrile oxide structure of fulminic acid and the fulminates by Pauling and Hendricks, 8 Barnard and Neitzel 9 prepared a fulminate-ferrihemoglobin compound. Hydrogen selenide derivatives of ferrihemoglobin and ferriheme were also prepared. 10 Combinations between thiocyanate and ferrihemoglobin and between cyanate and ferrihemoglobin were shown to exist by Jung 11 and Hecht 12 respectively. Thiocyanic and cyanic acids are now known to be hydroacids. 13 A cyanamide derivative of ferriheme 14 and ferrihemoglobin 15 have also been prepared. In the description of the cyanamide compounds, the terms ferride-heme (in place of hemoferride), ferridehemo-chromogen and ferridehemoglobin were introduced in order to adapt to these substances, the system of nomenclature proposed by Pauling and Coryell 16 for the blood pigment derivatives.

It is assumed that the ferridehemoglobin engendering combination between ferrihemoglobin and hydro-acid anions is conditioned by the comparatively small ionic diameter of the latter. Of the relatively limited class of acids which are not oxy-acids, the majority do combine with ferrihemoglobin. Potentiality for this type of combination seems to be restricted to the smaller members of the class; the halides with the exception of the smallest, fluoride, do not so combine.