Hydroxyl Radical

Example 4

Octadecanoate Functionalized Core (IMS 018 H)

To a round bottom flask was added one or more of the following “core” compounds: tripentaerythritol (“H”) made from the above cores. These were dissolved in tetrahydrofuran. 1.1 molar equivalents (per —OH of the hydroxyl terminated cores or dendrimers) of Octadecanoic Acid were added to the solution of cores. To these reagents were added 1.2 molar equivalents (per —OH of the hydroxyl terminated cores or dendrimers) of dicyclohexylcarbodiimide and 0.1 molar equivalents (per —OH of hydroxyl-terminated core or of dendrimer) of 4-dimethylaminopyridine (DMAP).

The reaction mixture was stirred vigorously for approximately 12 hours at standard temperature and pressure. The reaction was monitored by MALDI-TOF MS to determine completion of the reaction for each of the cores present in the reaction. After complete esterification is observed by MALDI-TOF MS, the flask contents were transferred to a separatory funnel, diluted with dichloromethane, extracted twice with 1M aqueous NaHSO₄ (sodium bisulfate) and extracted twice with 1M aqueous NaHCO₃ (sodium bicarbonate). The organic layer was reduced in vacuo to concentrate the sample. A MALDI-TOF MS spectra of the purified product confirmed the purity of the mixture of esterified products and is shown in FIG. 11.

FIG. 11 shows MALDI-TOF MS data for IMS 018 H, the product of octadecanoic acid functionalization of core H (IMS018H).

Example 125

[Figure (not displayed)]

Methyl 4-((5-(benzyloxy)-2-methoxyphenyl)(ethyl)amino)butanoate (184). 5-(Benzyloxy)-N-ethyl-2-methoxyaniline (146) (0.681 g, 2.65 mmol), DIEA (0.92 mL, 5.3 mmol), and methyl 4-iodobutyrate (0.72 mL, 5.3 mmol) in DMF (5 mL) were stirred at 70° C. for 5 days. The reaction mixture was cooled to rt, diluted with EtOAc (60 mL), washed with water (4×50 mL), brine (75 mL), dried over Na₂SO₄ and evaporated. The residue was purified by chromatography on a silica gel column (2.5×30 cm bed, packed with CHCl₃), eluant: 5% MeOH in CHCl₃ to get compound 184 (0.72 g, 76%) as a dark amber oil.

Methyl 4-(ethyl(5-hydroxy-2-methoxyphenyl)amino)butanoate (186). Ester 184 (0.72 g, 2.0 mmol) was stirred under reflux with 6 mL of water and 6 mL of conc HCl for 1.5 hrs and then evaporated to dryness to give acid 185 as a brown gum. The crude acid was dissolved in 50 mL of methanol containing 1 drop (cat.) of methanesulfonic acid ant the solution was kept for 2 hrs at rt. After that the mixture was concentrated in vacuum and the residue was mixed with 20 mL of saturated NaHCO₃. The product was extracted with EtOAc (3×40 mL). The extract was washed with brine (40 mL), dried over Na₂SO₄ and evaporated. The residue was purified by chromatography on a silica gel column (2.5×30 cm bed, packed with CHCl₃), eluant: 5% MeOH in CHCl₃ to get compound 186 (0.444 g, 83%) as a brown oil.

N-(6-(dimethylamino)-9-(4-(ethyl(4-methoxy-4-oxobutyl)amino)-2-hydroxy-5-methoxyphenyl)-3H-xanthen-3-ylidene)-N-methylmethanaminium chloride (187). To a stirred suspension of tetramethylrhodamine ketone 101 (0.234 g, 0.830 mmol) in 10 mL of dry chloroform was added oxalyl chloride (72 μL, 0.82 mmol) upon cooling to 0-5° C. The resulting red solution was stirred for 0.5 h at 5° C., and the solution of compound 186 (0.222 g, 0.831 mmol) in dry chloroform (5 mL) was introduced. The reaction was allowed to heat to rt, stirred for 72 h, diluted with CHCl₃ (100 mL and washed with sat. NaHCO₃ solution (2×30 mL) The organic layer was extracted with 5% HCl (3×25 mL). The combined acid extract was washed with CHCl₃ (2×15 mL; discarded), saturated with sodium acetate and extracted with CHCl₃ (5×30 mL). The extract was washed with brine (50 mL), dried over Na₂SO₄ and evaporated. The crude product was purified by chromatography on silica gel column (2×50 cm bed, packed with CHCl₃/MeOH/AcOH/H₂O (100:20:5:1)), eluant: CHCl₃/MeOH/AcOH/H₂O (100:20:5:1) to give the product 187 (0.138 g, 29%) as a purple solid.

4-((4-(6-(dimethylamino)-3-(dimethyliminio)-3H-xanthen-9-yl)-5-hydroxy-2-methoxyphenyl)(ethyl)amino)butanoate (188). Methyl ester 187 (0.136 g, 0.240 mmol) was dissolved in 5 mL of 1M KOH (5 mmol). The reaction mixture was kept at rt for 1.5 hrs and the acetic acid (1 mL) was added. The mixture was extracted with CHCl₃ (4×30 mL), and combined extract was washed with brine (20 mL), filtered through the paper filter and. The crude product was purified by chromatography on silica gel column (2×50 cm bed, packed with MeCN/H₂O (4:1)), eluant: MeCN/H₂O/AcOH/(4:1:1) to give the product 188 (0.069 g, 98%) as a purple solid.

N-(6-(dimethylamino)-9-(4-((4-(2,5-dioxopyrrolidin-1-yloxy)-4-oxobutyl)(ethyl)amino)-2-hydroxy-5-methoxyphenyl)-3H-xanthen-3-ylidene)-N-methylmethanaminium chloride (189). To a solution of the acid 188 (69 mg, 0.12 mmol) in DMF (2 mL) and DIEA (58 μL, 0.33 mmol) was added N-hydroxysuccinimide trifluoroacetate (70 mg, 0.33 mmol). The reaction mixture was stirred for 30 min, diluted with chloroform (100 mL) and washed with water (5×50 mL), brine (50 mL), filtered through paper and concentrated in vacuum. The crude product was purified by precipitation from CHCl₃ solution (5 mL) with ether (20 mL) to give compound 189 (55 mg, 67%) as a purple powder.

Example 8

Cyclohexene (1a) and polar organic solvent (as mentioned in Table 1) in (1:2 to 1:10 weight ratio with respect to the substrate) was taken in to a 60 ml vessel. Further, the hybrid photocatalyst was added and the resulting mixture was saturated with CO₂ by purging at 1 atm pressure. The reaction vessel was sealed and irradiated with 20 W LED light (Model No. HP-FL-20 W-F, Hope LED Opto-Electric CO., Ltd) for 24 h. The conversion of the olefin and selectivity of the α,β-unsaturated hydroxyl or carbonyl compound as determined by GC-FID and GC-MS is mentioned in the Table 1 (entry 8-13).