[Differences between phthaleins and sulfonphthaleins].
Differences in color and molecular structure between phthalein-pigments and sulfonphthalein-pigments were investigated using X-ray crystallography and absorption spectrophotometry of their aqueous solutions. The molecular structure of sulfonefluorescein (H2+SF-) was determined as a zwitter ion, 2-(3-hydroxonio-6-hydroxy-3H-xanthen-9-yl)benzenesulfonate. The absorption spectra of H2+SF- demonstrated the dissociation profile of a dibasic acid, while those of fluorescein (H2FL) indicated a tribasic acid and further, at pH > 10, SF2- and FL2-, while at pH < 0, H2+SF- and H3+FL to be dominant. The spectra of H2+SF- were analyzed to obtain the values of pK1 and pK2 together with the spectrum of HSF-. Similarly, from the spectra of H3+FL the values of pK1, pK2 and pK3 together with the spectra of HFL- and H2FL were obtained. Further by adding 1/5 of the H3+FL spectrum to 2/15 of HFL- spectrum, an indicated spectrum as that of H2FL was obtained. From these results, the features of dissociation of H2SF- and H3+FL were estimated. The molecular structure of phenolsulfonphtalein (H2PS-) was determined as a zwitter-ion, alpha-(4-hydroxonio-2,5-cyclohexadiene-1-ylidene)-alpha- (4-hydroxyphenyl)-2-toluenesulfonate. The absorption spectra of H2PS- demonstrated that H2PS-, HPS- and PS2- became dominant at pH << 0, pH = 4 and pH > 11, respectively. On the contrary, phenolphthalein (H2PP) displayed only one type of absorption spectrum in the visual region, the shape of which was similar to that of PS2- while the molar extinction coefficient was smaller. The spectra were analyzed to obtain the values of pK1 = 9.05 and pK2 = 9.50. The spectra also demonstrated a slow addition reaction of OH- to PP2- and pK3 = 12 was obtained by measuring the absorbance after equilibration. From these results, the features of dissociation and coloration of H2+PS- and H2PP were estimated.
Tamura
Z
Z
School of Pharmaceutical Sciences, Showa University, Tokyo, Japan.
Maeda
M
M
D003116:Color; D004396:Coloring Agents; D018360:Crystallography, X-Ray; D019793:Fluorescein / Q000737:chemistry; D005452:Fluoresceins / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D015394:Molecular Structure; D010635:Phenolphthaleins / Q000737:chemistry; D010637:Phenolsulfonphthalein / Q000737:chemistry; D012996:Solutions; D013054:Spectrophotometry, Atomic; D014867:Water
D004396:Coloring Agents; D005452:Fluoresceins; D010635:Phenolphthaleins; D012996:Solutions; D014867:Water; C110302:sulfonefluorescein; D010637:Phenolsulfonphthalein; D019793:Fluorescein