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Abstract

Condensations between 3-X-2,4-dimethylpyrroles (X = H, CH3, C2H5, and CO2C2H5) and acyl chlorides gave derivatives of 3,5,3′,5′-tetramethylpyrromethene (isolated as their hydrochloride salts): 6-methyl, 6-ethyl, 4,4′,6-trimethyl, 4,4′-diethyl-6-methyl, and 4,4′-dicarboethoxy-6-ethyl derivatives for conversion on treatment with boron trifluoride to 1,3,5,7-tetramethylpyrromethene–BF2 complex (TMP–BF2) and its 8-methyl (PMP–BF2), 8-ethyl, 2,6,8-trimethyl (HMP–BF2),2,6,-diethyl-8-methyl (PMDEP–BF2), and 2,6-dicarboethoxy-8-ethyl derivatives. Chlorosulfonation converted, 1,3,5,7,8-pentamethylpyrromethene–BF2 complex to its 2,6-disulfonic acid isolated as the lithium, sodium (PMPDS–BF2), potassium, rubidium, cesium, ammonium, and tetramethylammonium disulfonate salts and the methyl disulfonate ester. Sodium 1,3,5,7-tetramethyl-8-ethylpyrromethene-2,6-disulfonate–BF2 complex was obtained from the 8-ethyl derivative of TMP–BF2. Nitration and bromination converted PMP–BF2 to its 2,6-dinitro-(PMDNP–BF2) and 2,6-dibromo- derivatives. The time required for loss of fluorescence by irradiation from a sunlamp showed the following order for P–BF2 compounds (10−3 to 10−4 M) in ethanol: PMPDS–BF2, 7 weeks; PMP–BF2, 5 days; PMDNP–BF2, 72 h; HMP–BF2, 70 h; and PMDEP–BF2, 65 h. Under similar irradiation PMPDS–BF2 in water lost fluorescence after 55 h. The dibromo derivative was inactive, but each of the other pyrromethene–BF2 complexes under flashlamp excitation showed broadband laser activity in the region λ 530–580 nm. In methanol PMPDS–BF2 was six times more resistant to degradation by flashlamp pulses than was observed for Rhodamine-6G (R-6G). An improvement (up to 66%) in the laser power efficiency of PMPDS–BF2 (10−4 M in methanol) in the presence of caffeine (a filter for light <300 nm) was dependent on flashlamp pulse width (2.0 to 7.0 μsec).