Potassium Carbonate → HCID 57856000, compound
Reaction equation
[Cl:1][C:2]1[C:3]([F:15])=[C:4]([CH:8]=[C:9]([N+:12]([O-:14])=[O:13])[C:10]=1F)[C:5]([OH:7])=[O:6].C([O-])([O-])=O.[K+].[K+].[CH3:22][Si:23]([CH3:28])([CH3:27])[CH2:24][CH2:25][SH:26].[NH4+].[Cl-]>CCO.O>[Cl:1][C:2]1[C:3]([F:15])=[C:4]([CH:8]=[C:9]([N+:12]([O-:14])=[O:13])[C:10]=1[S:26][CH2:25][CH2:24][Si:23]([CH3:28])([CH3:27])[CH3:22])[C:5]([OH:7])=[O:6]Participants
Conditions
- Temperature
- 50 °C
Procedure
To a mixture of 3.52 g (16.96 mmol) of 3-chloro-2,4-difluoro-5-nitro-benzoic acid (prepared as described in WO 03/077914) in 70 mL of EtOH, is added 6.56 g (47.48 mmol, 2.8 eq.) of K2CO3 dissolved in 30 mL of H2O. Then, 2.67 mL (16.96 mmol) of 2-(trimethylsilyl)ethanethiol are added in 10 minutes. The mixture is stirred at 50° C. during 1 h and then cooled to ambient temperature. After addition of a saturated NH4Cl aqueous solution, the product is extracted with EtOAc (3 times). The regrouped organic phases are dried with Na2SO4, filtered and evaporated. The crude 3-chloro-2-fluoro-5-nitro-4-(2-trimethylsilanyl-ethylsulfanyl)-benzoic acid is contaminated by 3-chloro-5-nitro-2,4-bis-(2-trimethylsilanyl-ethylsulfanyl)-benzoic acid. NMR integrals indicated a ratio 74:26 in favour of the desired compound. 1H-NMR of 3-chloro-2-fluoro-5-nitro-4-(2-trimethylsilanyl-ethylsulfanyl)-benzoic acid (CDCl3, 300 MHz): 0.04 (s, 9H), 0.76-0.81 (m, 2H), 2.90-2.94 (m, 2H), 7.93 (d, 1H) ppm. The mixture is used directly in the next step without further purification.
Workup
- temperaturecooled to ambient temperature
- extractionthe product is extracted with EtOAc (3 times)
- dry with materialThe regrouped organic phases are dried with Na2SO4
- filtrationfiltered
- customevaporated
- customThe mixture is used directly in the next step without further purification
Sources & evidence
- ORD record
- ord-4064ebaeaef94fd6b4a5745ca888b575
- Source dataset
- uspto-grants-2013_11
- Patent number
- US08580785B2
Reaction notes
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