Chlorosuccinimide → (4-Chloromethylsulfanyl-2,6-dimethylphenoxy)triisopropylsilane
Reaction equation
[CH3:1][C:2]1[CH:18]=[C:17]([S:19][CH3:20])[CH:16]=[C:15]([CH3:21])[C:3]=1[O:4][Si:5]([CH:12]([CH3:14])[CH3:13])([CH:9]([CH3:11])[CH3:10])[CH:6]([CH3:8])[CH3:7].[Cl:22]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[Cl:22][CH2:20][S:19][C:17]1[CH:18]=[C:2]([CH3:1])[C:3]([O:4][Si:5]([CH:12]([CH3:14])[CH3:13])([CH:6]([CH3:7])[CH3:8])[CH:9]([CH3:10])[CH3:11])=[C:15]([CH3:21])[CH:16]=1Participants
Procedure
To a stirring solution of (2,6-dimethyl-4-methylsulfanyl-phenoxy)triisopropylsilane (2.18 g, 6.72 mmol) in CCl4 (25 mL) at room temperature was added N-chlorosuccinimide (0.99 g, 7.39 mmol). The reaction mixture was stirred at room temperature for 16 hrs and filtered through a Celite plug. The solvent was removed under reduced pressure to afford crude (4-chloromethylsulfanyl-2,6-dimethylphenoxy)triisopropylsilane as an oil (2.4 g, 100%). This crude oil was dissolved into phosphorous acid triethyl ester (1.5 mL). It was heated at 180° C. for 30 min by microwave. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel, eluting with ethyl acetate-hexanes (1:1) to afford diethyl (3,5-dimethyl-4-triisopropylsilanyloxy-phenylsulfanyl)methylphosphonate as a yellow oil (1.6 g, 52%): 1H NMR (200 MHz, DMSO-d6): δ 7.09 (s, 2 H), 4.98 (m, 4 H), 3.31 (d, J=13.8 Hz, 2 H), 2.17 (s, 6 H), 1.25 (m, 9 H), 1.09 (d, J=7.0 Hz, 18 H). TLC conditions: Uniplate silica gel, 250 microns; Mobile phase=ethyl acetate/Hexanes (2:3); Rf=0.45.
Workup
- filtrationfiltered through a Celite plug
- customThe solvent was removed under reduced pressure
Sources & evidence
- ORD record
- ord-7835fa6d91154098ac4bef7808c56d73
- Source dataset
- uspto-grants-2009_04
- Patent number
- US07514419B2
Reaction notes
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