The N-carboxypropylsubstituted cyanine dye 2a (0.6080 g, 0.00131 mole) and merocyanine dye 2b (0.371 g, 0.001 mole) were sonicated in 700 mL of dry dichloromethane at room temperature under argon for 2.5 hr to produce a very fine suspension. Tributylamine (1.143 g, 1.47 mL, 0.0062 mole) and 4-(dimethylamino)pyridine (DMAP) (0.0366 g, 0.0003 mole) were added successively to the reaction mixture and sonicated for another 2 min. Then 2-chloro-1-methylpyridinium iodide (0.7921 g, 0.0031 mole) was added to the reaction mixture all at once and the resulting reaction mixture was sonicated for an additional 5 hr at room temperature. As the reaction progressed, the mixture turned from deep yellow to deep orange and finally became nearly homogeneous. The solvent was removed completely on a rotary evaporator with the water bath temperature kept below 40° C. The orange-colored thick residue was triturated with anhydrous ether (100 mL) and a few drops of dichioromethane. The insoluble crude product was collected on a sintered glass funnel, washed with anhydrous ether (2×25 mL) and air dried. The yield was 1.80 g, 0.855g in excess of the theoretical yield because of the presence of unreacted 2-chloro-1-methylpyridinium iodide and tributylammonium hydrochloride. These materials were removed by sonicating the crude solid material in 50 mL of distilled water for 5 min and collecting the insoluble binary dye, which now weighed 0.9586 g (ca 100% yield) after drying in a vacuum oven at 40° C. Two more batches were prepared under the same reaction conditions. Crude products from each batch, after water treatment, were combined for further purification by flash column chromatography. The first purification on flash grade silica gel was done by eluting with tetrahydrofuran. About 3.0 g of crude material gave 1.2 g of cleaner product. Its TLC indicated a small amount of starting merocyanine. The whole amount was coated on 10 g of regular column grade silica gel in 100 mL of dichloromethane. The dry coat, which was obtained after removing the solvent, was loaded on 60 g of flash column grade silica gel. It was eluted with a 98:2 mixture of diclilorometliane and 2-propanol with the application of 5-10 lbs pressure of nitrogen gas. The first fraction (purple) and second fraction (light brownish yellow) were discarded. The third fraction, which was obtained from a brownish red band portion on the column, was evaporated on a rotary evaporator while the water bath temperature was kept below 40° C. The residue was triturated with anhydrous ether (200 mL), then collected by filtration, washed with anhydrous ether and air dried. The yield was 0.375 g. An ionogram showed it to be a cationic dye. Infrared, 1HNMR, and field desorption mass spectrophotollietric measurements were consistent with the proposed structure. The dye had a λmax of 414 nm (MeOH) with εmax of 12.97×104 (dihydrate). Elemental analysis: Calcd for C40 H38Cl2N5O6S2I·2H2O: C, 48.84; H, 4.2; N, 7.10; S, 6.50. Found: C, 48.70; H, 3.9; N, 6.80; S, 6.60.
