6-BROMO-1,2,3,4-TETRAHYDROQUINOLINE

General procedure: To a dry vial containing 8-methoxyquinoline, 1 (0.048 g, 0.3 mmol), Me2PhSiH (185 μL, 1.2mmol) and ethanol (70 μL, 1.2 mmol), Au/TiO2 (60 mg, 1.0 molpercent) was added. The Au contentin catalyst was ~1 wtpercent. The mixture was heated to 70 oC and the progress of reaction wasmonitored by TLC and GC. After 15 min (100percent conversion), ethanol (1 mL) was added and theresulting slurry was filtered under reduced pressure through a short pad of silica gel with the aidof ethanol (2-3 mL) to withhold the supported catalyst. The filtrate was evaporated undervacuum and the residue was chromatographed (n-hexane/ethyl acetate, 10:1) to afford 8-methoxy-1, 2, 3, 4-tetrahydroquinoline (1a) (41 mg, 84percent yield).NBS (28 g, 158 mmol) was added to a solution of 1, 2, 3, 4-tetrahydroquinoline (20 g, 150.16 mmol) in carbon tetrachloride (200 mL). The resulting solution was stirred for 3 h at 0°C, extracted with dichloromethane(3 x 50 mL) and concentrated in vacuo to give a residue, which was applied onto a silica gel column with 1 percent ethyl acetate in petroleum ether to give 6-bromo- 1 , 2, 3, 4-tetrahydroquinoline as a yellow solid (11 g, 35percent).LC/MS(ES, m/z):[M+H]Reaction step 1 To a solution of 1, 2, 3, 4-tetrahydroquinoline (2.0 g, 15.0 mmol) in DMF (20 mL), was added NBS (2.67 g, 15.0 mmol) in one portion. The mixture was stirred at 0 for 1 h. It was then extracted with EA, the combined organic layers were washed with brine, dried over Na2SO4, concentrated and purified by flash chromatography to give 6-bromo-1, 2, 3, 4- tetrahydroquinoline as a yellow oil (3.1 g, 97%). LC-MS (ESI): m/z (M+H) = 212.08/214.08.NBS (28 g, 158 mmol) was added to a solution of 1, 2, 3, 4-tetrahydroquinoline (20 g, 150.16 mmol) in carbon tetrachloride (200 mL). The resulting solution was stirred for 3 h at 0C, extracted with dichloromethane(3 x 50 mL) and concentrated in vacuo to give a residue, which was applied onto a silica gel column with 1 % ethyl acetate in petroleum ether to give 6-bromo- 1 , 2, 3, 4-tetrahydroquinoline as a yellow solid (11 g, 35%).LC/MS(ES, m/z):[M+H]+ 212.1'H-NMR (300 MHz, CDC13) delta 7.03 - 7.07 (m, 2H), 6.35 - 6.38 (m, 1H), 3.51 - 3.55 (m, 2H), 2.73- 2.80 (m, 2H), 1.89 - 1.99 (m, 2H)Step 1: To a solution of 1, 2, 3, 4-tetrahydroquinoline (100 mg) in N, N-dimethylformamide (1 ml), a solution of N-bromosuccinimide (134 mg) in N, N-dimethylformamide (1 ml) was added dropwise under ice cooling and stirred at the same temperature for 1 hour. The reaction mixture was diluted with water and extracted with ethyl acetate. The extracted organic layer was washed sequentially with water and brine, dried over anhydrous magnesium sulfate and then filtered to remove the desiccant, followed by distilling off the solvent under reduced pressure to give To a stirred solution of 1 , 2, 3, 4-tertrahydroquinoline, 3 (10.0 g, 75 mmol) in DMF (100 mL) was added NBS (17.4 g, 98 mmol) in portions at 0 C and the mixture was stirred for 2 h. The progress of the reaction was monitored by TLC (TLC system: 10 % EtO Ac/Pet ether, Rf value: 0.5). After completion of the reaction, the reaction was quenched with water and extracted with ethyl acetate (2 x 200 mL). The combined organic layers were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure to afford crude product. The crude product was purified over silica gel (100-200 mesh) column chromatography by eluting with 3 % EtO Ac/Pet ether to give 6-bromo-l , 2, 3, 4-tetrahydroquino line, 4 as a light yellow liquid. 1HNMR (400 MHz, CDCl3) delta: 7.05-7.01 (m, 2 H), 6.36 (d, 1 H, J = 8.8 Hz), 3.29-3.27 (m, 2 H), 2.72 (t, 2 H, J = 6 Hz), 1.94-1.89 (m, 2 H).Reaction step 1. Synthesis of Reaction step 1 Synthesis of To a solution of chlorosulfonyl isocyanate (14g, 10mmol) in dichloromethane (20mL) at 0C was added dropwise tert-butanol (0.74g, 10mmol). The mixture was stirred at 0C for 5min, then warm to room temperature for 3h to give the BOC protected amino-sulfonyl-chloride. The mixture was then carefully added over 30min to a solution of

Molecular Weight:212.09
XLogP3:3
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Exact Mass:210.99966
Monoisotopic Mass:210.99966
Topological Polar Surface Area:12
Heavy Atom Count:11
Complexity:138
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes