1911 Encyclopædia Britannica/Fluorescein

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FLUORESCEIN, or Resorcin-Phthalein, C20H12O5, in chemistry, a compound discovered in 1876 by A. v. Baeyer by the condensation of phthalic anhydride with resorcin at 195–200° C. (Ann., 1876, 183, p. 1). The two reacting substances are either heated alone or with zinc chloride for some hours, and the melt obtained is boiled out with water, washed by dilute alcohol, extracted by means of sodium hydrate, and the solution so obtained is precipitated by an acid. The precipitate is well washed with water and then dried. By repeating this process two or three times, the fluorescein may be obtained in a very pure condition. It forms a yellow amorphous powder, insoluble in water but soluble in alcohol, and crystallizing from the alcoholic solution in small dark red nodules. It is readily soluble in solutions of the caustic alkalis, the solution being of a dark red colour and showing (especially when largely diluted with water) a brilliant green fluorescence. It was so named on account of this last character. By brominating fluorescein in glacial acetic acid solution, eosin (tetrabromfluorescein) is obtained, the same compound being formed by heating 3.5–dibrom-2.4–dioxybenzoylbenzoic acid above its melting point (R. Meyer, Ber., 1895, 28, p. 1576). It crystallizes from alcohol in yellowish red needles, and dyes silk, wool, and mordanted cotton a fine pink colour. When heated with caustic alkalis it yields dibromresorcin and dibrommonoresorcin-phthalein. The corresponding iodo compound is known as erythrosin. Fluorescein is readily nitrated, yielding a di- or tetra-nitro compound according to conditions. The entrance of the negative nitro group into the molecule weakens the central pyrone ring in the fluorescein nucleus and the di- and tetra-nitro compounds readily yield hydrates (see J.T. Hewitt and B.W. Perkins, Jour. Chem. Soc., 1900, p. 1326). By the action of ammonia or amines the di-nitro fluoresceins are converted into yellow dyestuffs (F. Reverdin, Ber., 1897, 30, p. 332). Other dyestuffs obtained from fluorescein are safrosine or eosin scarlet (dibromdinitrofluorescein) and rose Bengal (tetraiodotetrachlorfluorescein).

On fusion with caustic alkali, fluorescein yields resorcin, C6H4(OH)2, and monoresorcin phthalein (dioxybenzoylbenzoic acid), (HO)2C6H3·CO·C H4·COOH. With zinc dust and caustic soda it yields fluorescin. By warming fluorescein with excess of phosphorus pentachloride it yields fluorescein chloride, C20H10O3Cl2 (A. Baeyer), which crystallizes from alcohol in small prisms, melting at 252° C. When heated with aniline and aniline hydrochloride, fluorescein yields a colourless anilide (O. Fischer and E. Hepp, Ber., 1893, 26, p. 2236), which is readily methylated by methyl iodide and potash to a fluoresceinanilidedimethyl ether, which when heated for six hours to 150° C. with acetic and hydrochloric acids, is hydrolysed and yields a colourless fluoresceindimethyl ether, which melts at 198° C. On the other hand, by heating fluorescein with caustic potash, methyl iodide and methyl alcohol, a coloured (yellow) dimethyl ether, melting at 208° C. is obtained (Fischer and Hepp). By heating the coloured dimethyl ether with caustic soda, the monomethyl ether is obtained (O. Fischer and E. Hepp, Ber., 1895, 28, p. 397); this crystallizes in triclinic tables, and melts at 262° C. It is to be noted that the colourless monomethyl ether fluoresces strongly in alkaline solution, the dimethyl ether of melting point 208° fluoresces only in neutral solution (e.g., in alcoholic solution), and the dimethyl ether of melting point 198° C. only in concentrated hydrochloric or sulphuric acid solution (Fischer and Hepp). Considerable discussion has taken place as to the position held by the hydroxyl groups in the fluorescein molecule, C. Graebe (Ber., 1895, 28, p. 28) asserting that they were in the ortho position to the linking carbon atom of the phthalic anhydride residue. G. Heller (Ber., 1895, 28, p. 312), however, showed that monoresorcin-phthalein when brominated in glacial acetic acid gives a dibrom derivative which, with fuming sulphuric acid, yields dibromxanthopurpurin (1.3-dioxy-2.4–dibromanthraquinone), a reaction which is only possible if the fluorescein (from which the monoresorcin-phthalein is derived) contains free hydroxyl groups in the para position to the linking carbon atom of the phthalic anhydride residue.