1,10-Phenanthroline → 1-[2-(2-Trifluoromethylphenylsulfanyl)phenyl]piperazine

温度

55 °C

To a solution of 2-trifluoromethylthiophenol (1.75 g, 9.8 mmol) in a 1:1 mixture of tetrahydrofuran/dimethylformamide (30 mL), sodium hydride (7.4 mmol, 60% in mineral oil) was carefully added at room temperature (Caution: Generation of hydrogen). The mixture was stirred for an additional 30 min after the generation of hydrogen had ceased. Subsequently, 4-({4-[6-(2-chloro-phenyl)-η5-cyclopentadienyliron(II)]piperazin-1-yl}carbonyloxymethyl)phenoxymethyl polystyrene hexafluorophosphate (3.5 g, 2.45 mmol) was added and the mixture was stirred at 55° C. for 12 h. After cooling to room temperature, the resin was filtered off and washed with tetrahydrofuran (2×50 mL), tetrahydrofuran/water (1:1) (2×50 mL), N,N-dimethylformamide (2×50 mL), water (2×50 mL), methanol (3×50 mL), tetrahydrofuran (3×50 mL), and subsequently with methanol and tetrahydrofuran (each 50 mL, 5 cycles). Finally, the resin was washed with dichloromethane (3×50 mL) and dried in vacuo (25° C., 12 h) to yield a dark orange resin. The thus obtained resin and a 0.5 M solution of 1,10-phenanthroline in 3:1 mixture of pyridine/water (20 mL) was placed in light-transparent reactor tube. The suspension was agitated by rotation under irradiation with visible light for 12 h. The resin was filtered and washed with methanol (2×25 mL), water (2×25 mL) and tetrahydrofuran (3×25 mL) until the washing solutions were colourless (approx. 5 cycles) and the irradiation procedure was repeated until decomplexation was complete (approx. 5 cycles). After the decomplexation was completed, the resin was washed with dichlormethane (3×25 mL) and dried in vacuo (25° C., 12 h) to obtain a light brown resin. 100 mg (77 μmol) of the thus obtained resin were suspended in a 1:1 mixture of trifluoroacetic acid and dichlormethane (2 mL) and stirred at room temperature for 2 h. The resin was filtered off and washed with methanol (1×0.5 mL) and dichloromethane (1×0.5 mL). The filtrates were collected and the volatile solvents evaporated in vacuo. The crude product was purified by preparative LC-MS and subsequently by ion-exchange chromatography. LC/MS (m/z) 339 (MIT); RT=2.39; purity (UV, ELSD): 92%, 100%; overall yield: 1 mg (4%).

1. temperatureAfter cooling to room temperature
2. filtrationthe resin was filtered off
3. washwashed with tetrahydrofuran (2×50 mL), tetrahydrofuran/water (1:1) (2×50 mL), N,N-dimethylformamide (2×50 mL), water (2×50 mL), methanol (3×50 mL), tetrahydrofuran (3×50 mL)
4. washFinally, the resin was washed with dichloromethane (3×50 mL)
5. customdried in vacuo (25° C., 12 h)
6. customto yield a dark orange resin
7. customwas placed in light-transparent reactor tube
8. stirringThe suspension was agitated by rotation under irradiation with visible light for 12 h
9. filtrationThe resin was filtered
10. washwashed with methanol (2×25 mL), water (2×25 mL) and tetrahydrofuran (3×25 mL) until the washing solutions
11. customthe irradiation procedure
12. washthe resin was washed with dichlormethane (3×25 mL)
13. customdried in vacuo (25° C., 12 h)
14. customto obtain a light brown resin
15. stirringstirred at room temperature for 2 h
16. filtrationThe resin was filtered off
17. washwashed with methanol (1×0.5 mL) and dichloromethane (1×0.5 mL)
18. customThe filtrates were collected
19. customthe volatile solvents evaporated in vacuo
20. customThe crude product was purified by preparative LC-MS and subsequently by ion-exchange chromatography
21. customRT=2.39

ORDレコード

ord-e263dd4e77384fe6b3e693c96de9be19

出典データセット

uspto-grants-2013_07

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08476279B2