Sodium Hydroxide → 4-(4-bromo-1-(3-chloro-2-methylbenzyl)-2-(trifluoromethyl)-1H-benzo[d]imidazol-6-yl)morpholine
Reaction equation
[Br:1][C:2]1[C:10]2[N:9]=[C:8]([C:11]([F:14])([F:13])[F:12])[N:7]([CH2:15][C:16]3[CH:21]=[CH:20][CH:19]=[C:18]([Cl:22])[C:17]=3[CH3:23])[C:6]=2[CH:5]=[C:4]([NH2:24])[CH:3]=1.[OH-].[Na+].Br[CH2:28][CH2:29][O:30][CH2:31][CH2:32]Br>[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[Br:1][C:2]1[C:10]2[N:9]=[C:8]([C:11]([F:14])([F:13])[F:12])[N:7]([CH2:15][C:16]3[CH:21]=[CH:20][CH:19]=[C:18]([Cl:22])[C:17]=3[CH3:23])[C:6]=2[CH:5]=[C:4]([N:24]2[CH2:32][CH2:31][O:30][CH2:29][CH2:28]2)[CH:3]=1Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 110 °C
Procedure
Into a 100 ml round bottomed flask charged with 4-bromo-1-(3-chloro-2-methylbenzyl)-2-(trifluoromethyl)-1H-benzo[d]imidazol-6-amine (3.1 g, 7.40 mmol) and tetrabutylammonium iodide (0.137 g, 0.370 mmol) was added 6N sodium hydroxide (18.51 ml, 111 mmol) and 1-bromo-2-(2-bromoethoxy)ethane (1.87 ml, 14.81 mmol). The reaction was heated to 110° C. and was monitored by LCMS. The reaction was complete after 2 h. The reaction was cooled to RT and the mixture was extracted with ethyl acetate (3×25 mL). The combined organic phase was washed with brine (30 mL), the organic extracts were combined, concentrated in vacuo, and the residue was purified by flash chromatography on silica gel eluted with a solution of (2N ammonia in methanol)/chloroform (0% to 10%). The fractions containing product were combined, then concentrated in vacuo to provide the desired product (1.62 g, 3.31 mmol, 44.8% yield) as a brown solid. NMR & LCMS were consistent with the structure. MS (ES+) m/e: 487.1, 488.1 [M+H]+; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 2.42 (s, 3H) 3.03-3.21 (m, 4H) 3.78-3.89 (m, 4H) 5.43 (s, 2H) 6.28 (d, J=7.58 Hz, 1H) 6.38 (d, J=2.02 Hz, 1H) 6.99 (t, J=7.96 Hz, 1H) 7.29 (d, J=2.27 Hz, 1H) 7.34 (d, J=7.83 Hz, 1H)
Workup
- temperatureThe reaction was cooled to RT
- extractionthe mixture was extracted with ethyl acetate (3×25 mL)
- washThe combined organic phase was washed with brine (30 mL)
- concentrationconcentrated in vacuo
- customthe residue was purified by flash chromatography on silica gel
- washeluted with a solution of (2N ammonia in methanol)/chloroform (0% to 10%)
- additionThe fractions containing product
- concentrationconcentrated in vacuo
Sources & evidence
- ORD record
- ord-bcef0154e88a448b8f466dcc1fd03ac4
- Source dataset
- uspto-grants-2014_07
- Patent number
- US08778937B2
Reaction notes
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