Tietze, Ernst; Bayer, Otto published the artcile< Sulfonic acids of pyrene and their derivatives>, Application In Synthesis of 112-63-0, the main research area is .
Pyrene (I) in 6 parts C2Cl4, cooled to 0°, treated with the calculated quantity of ClSO3H in C2Cl4 at 0-5° and stirred 15-20 h. at 10-20°, decomposed with ice-H2O, the C2Cl4 removed by distillation in vacuo, the solution filtered hot and treated with a hot solution of the calculated quantity of Na2SO4, gives 90-2% of Na pyrene-3-sulfonate (II). II (61 g.) in 500 cc. AcOH and 17.5 g. of 80% HNO3, mixed and stirred 12 h. at 15-25°, give a NO2 compound, which is reduced by Fe in AcOH to an NH2 derivative (41 g.), yellow powder, whose aqueous solution shows an intense blue fluorescence; the solution is easily diazotized and couples with R salt to a dull-violet dye. Addition of 202 g. of I to 500 g. H2SO4 (66° Bé) at 0° during 1 h. and allowing the mixture to stand 2 days at 15° give 45 g. I and after addition of NaCl 130 g. III; II (61 g.), added during 30 min. to 400 g. H2SO4 (66°Bé.) at 5-10° and stirred 1 h., gives 42% of di-Na pyrene-3,8-disulfonate (III), yellow powder soluble in H2O with a violet fluorescence. Heating 15 g. III with 38 g. KOH and 115 g. H2O for 6 h. at 260° (internal temperature) and 40 atm. gives 6 g. 3,8-dihydroxypyrene, which is sensitive to the air and was characterized as the di-Ac derivative, m. 222-4°. The mother liquor from III, treated with CaCO3, gives 7 g. of Ca pyrene-3,5-disulfonate (IIIA), the aqueous solution of which shows a pale blue fluorescence; this acid differs from the 3,8-isomer in the much greater solubility of the Na and Ca salts. II (76 g.) in 550 g. H2SO4.H2O at 5-10°, stirred 1 day at 15° poured onto ice, the H2SO4 removed by CaCO3 and neutralized with K2CO3, gives 12-15 g. of di-K mono-Na pyrene-3,5,8-trisulfonate, thick yellow prisms, which shows a strong violet fluorescence in aqueous solution When 924 g. of II are quickly added to 2600 g. H2SO4.H2O at 15-20° and, after cooling, treated with 2400 g. of 65% oleum at 20° and the mixture is stirred for 15 h. at 20°, the H2SO4 removed with CaCO3, the filtrate concentrated to 101., neutralized and treated with 20% NaCl, there results 80% of tetra-Na pyrene-3,5,8,10-tetrasulfonate (IV), a yellow powder; IV can be precipitated directly by addition of NaCl but the yield is lower. IV also results in 70% yield by adding 202 g. I to a mixture of 1300 g. H2SO4.H2O and 300 g. Na2SO4 at 58°, stirring 15 min., cooling to 50-5° and adding 800 g. of 65% oleum during 20 min. NaClO3 and HCl give the known 3,5,8,10-tetrachloropyrene, thus establishing the structure of IV. Refluxing 488 g. IV with 280 g. com. NaOH in 1400 cc. H2O for 18 h., adding 400 cc. com. HCl and neutralizing with HCO2H give on addition of 10% NaCl 340 g. of tri-Na 3-hydroxypyrene-5,8,10-trisulfonate (V), with 1 mol H2O, yellow needles. Heating 61 g. of IV with 610 cc. 22% NH4OH for 18 h. at 200-10° gives 22% of the 3-NH2 analog of V, greenish yellow prisms; the slightly acid solution shows an intense green fluorescence; the NH2 group may be diazotized. 3-Chloropyrene (24 g.) in 130 g. H2SO4.H2O and 30 g. Na2SO4, treated at 50-60° with 80 g. of 65% oleum, gives 41 g. of tri-Na 3-chloropyrene-5,8,10-trisulfonate; the Cl in this salt could not be replaced by NH2 by heating with NH4OH in an autoclave. Addition of 732 g. IV to a melt of 720 g. com. NaOH in 450 cc. H2O at 130° and heating 30 min. at 155°, 20 min. at 165° and 5 min. at 170° give 90% of di-Na 3,5-dihydroxypyrene-8,10-disulfonate (VI), yellow, which shows a green fluorescence in H2O. VI (219 g.) and 2.2 l. 10% H2SO4, heated 12 h. at 140-50°, give 90% (crude) of 3,5-dihydroxypyrene (VII) which, crystallized from AcOH, m. 220° (decomposition) and darkens in the air; di-Ac derivative, m. 154-5°; di-Me ether, m. 177-8°. IV (61 g.) in 450 cc. H2O and 37.5 g. 33% NaOH with 7 g. Zn dust, boiled 7 h., give 29-30 g. of di-Na pyrene-3,5-disulfonate (VIII), which may be purified through IIIA. VIII (40.6 g.) and 110 g. NaOH in 300 cc. H2O, heated 8 h. at 210-20°, give 22 g. of Na 3-hydroxypyrene-5-sulfonate, yellow, the aqueous solution of which shows a strong bluish green fluorescence. Heating VIII with NaOH at 250-60° for 15 h. gives VII. VIII (40.6 g.) and HNO3-H2SO4 at 18° for 20 h. give a 3,5-di-NO2 derivative, which is very soluble in H2O and is reduced to a di-NH2 derivative (27 g.). IV (366 g.) and 360 g. NaOH in 1080 g. H2O, heated 12 h. at 240-50°, give 32% of 3,5,8,10-tetrahydroxypyrene (IX), m. 236-8°; the aqueous solution shows a blue fluorescence; the concentrated H2SO4 solution is yellow with a green fluorescence; IX does not couple with diazo solutions Oxidation of IX with CrO2 gives a black powder. Tetra-Me ether of IX, pale brown, m. 172-3°; it could not be nitrated. Some of these compounds are dyes and the behavior with fabrics is given.
Justus Liebigs Annalen der Chemie published new progress about Dyes. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Application In Synthesis of 112-63-0.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics