m-Chloroperbenzoic acid → HCID 59434145, compound

HRID 508107Notes

Reaction equation

[F:1][C:2]1[CH:7]=[C:6]([N:8]([CH2:21][C:22]2[CH:23]=[C:24]([C:32]3[C:37]([CH3:38])=[CH:36][C:35]([O:39][CH:40]4[CH2:45][CH2:44][S:43](=[O:46])[CH2:42][CH2:41]4)=[CH:34][C:33]=3[CH3:47])[C:25]([O:28][CH:29]([CH3:31])[CH3:30])=[CH:26][CH:27]=2)[S:9]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[N+:18]([O-:20])=[O:19])(=[O:11])=[O:10])[CH:5]=[CH:4][C:3]=1[CH2:48][CH2:49][C:50]([O:52][CH2:53][CH3:54])=[O:51].ClC1C=CC=C(C(OO)=[O:63])C=1>C(OCC)(=O)C>[O:46]=[S:43]1(=[O:63])[CH2:44][CH2:45][CH:40]([O:39][C:35]2[CH:34]=[C:33]([CH3:47])[C:32]([C:24]3[C:25]([O:28][CH:29]([CH3:31])[CH3:30])=[CH:26][CH:27]=[C:22]([CH2:21][N:8]([S:9]([C:12]4[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=4[N+:18]([O-:20])=[O:19])(=[O:10])=[O:11])[C:6]4[CH:5]=[CH:4][C:3]([CH2:48][CH2:49][C:50]([O:52][CH2:53][CH3:54])=[O:51])=[C:2]([F:1])[CH:7]=4)[CH:23]=3)=[C:37]([CH3:38])[CH:36]=2)[CH2:41][CH2:42]1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of ethyl 3-(2-fluoro-4-{[(4′-hydroxy-6-isopropoxy-2′,6′-dimethylbiphenyl-3-yl)methyl][(2-nitrophenyl)sulfonyl]amino}phenyl)propanoate (0.59 g, 0.89 mmol), tetrahydro-2H-thiopyran-4-ol (0.12 g, 0.98 mmol) and triphenylphosphine (0.30 g, 1.16 mmol) in tetrahydrofuran (8 mL) was added diethyl azodicarboxylate (40% toluene solution, 0.53 mL, 1.16 mmol) under stirring at room temperature, and the mixture was stirred for 1 hr. To the reaction mixture were added reagents (tetrahydro-2H-thiopyran-4-ol, triphenylphosphine and diethyl azodicarboxylate) in the same amount as mentioned above, and the mixture was further stirred for 24 hr. The reaction mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=9/1-hexane/ethyl acetate=2/1) to give an oil (0.64 g). To a solution of the obtained oil in ethyl acetate (9 mL) was added m-chloroperbenzoic acid (70%, 0.44 g, 1.78 mmol) under stirring at 0° C., and the mixture was stirred at the same temperature for 2 hr. The reaction mixture was washed with 1 M aqueous sodium hydroxide solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=9/1-ethyl acetate) to give ethyl 3-(2-fluoro-4-{({6-isopropoxy-2′,6′-dimethyl-4′-[(1-oxidotetrahydro-2H-thiopyran-4-yl)oxy]biphenyl-3-yl}methyl)[(2-nitrophenyl)sulfonyl]amino}phenyl)propanoate (0.42 g, yield 61%, 2 steps) as a pale-yellow oil. To a solution of the obtained ethyl 3-(2-fluoro-4-{({6-isopropoxy-2′,6′-dimethyl-4′-[(1-oxidotetrahydro-2H-thiopyran-4-yl)oxy]biphenyl-3-yl}methyl)[(2-nitrophenyl)sulfonyl]amino}phenyl)propanoate (0.42 g, 0.54 mmol) in ethyl acetate (6 mL) was added m-chloroperbenzoic acid (70%, 0.15 g, 0.59 mmol) under stirring at 0° C., and the mixture was stirred at the same temperature for 1.5 hr. The reaction mixture was washed with 1 M aqueous sodium hydroxide solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=9/1-hexane/ethyl acetate=1/1) to give the title compound (0.40 g, yield 93%) as a colorless oil.

Workup

stirringthe mixture was stirred at the same temperature for 1.5 hr
washThe reaction mixture was washed with 1 M aqueous sodium hydroxide solution and saturated brine
dry with materialdried over anhydrous sodium sulfate
concentrationconcentrated under reduced pressure
customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=9/1-hexane/ethyl acetate=1/1)

Sources & evidence

ORD record: ord-63397e58d5dc455393fe559a5cc747a0
Source dataset: uspto-grants-2010_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07786165B2

Reaction notes

Loading…