Triethylamine → (4-(5-Bromo-2-chlorobenzyl)phenoxy)(tert-butyl)dimethylsilane

HRID 2174332Notes

Reaction equation

HRID 2174332 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:16])=[C:6]([CH:15]=1)[CH2:7][C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1.[C:17]([Si:21](Cl)([CH3:23])[CH3:22])([CH3:20])([CH3:19])[CH3:18].C(N(CC)CC)C>C(#N)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:16])=[C:6]([CH:15]=1)[CH2:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][Si:21]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:23])[CH3:22])=[CH:10][CH:9]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 28928tert-Butyldimethylsilyl chlorideHCID 574237514-((5-Bromo-2-chlorophenyl)methyl)phenol

Product 1

HCID 59747702(4-(5-Bromo-2-chlorobenzyl)phenoxy)(tert-butyl)dimethylsilaneYield 86.6%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a stirred suspension of 4-(5-bromo-2-chlorobenzyl)phenol (60 g, 0.202 mol) and tert-butylchlorodimethylsilane (37.9 g, 0.252 mol) in acetonitrile (300 mL) was added dropwise triethylamine (54.4 mL, 0.390 mol) so that the reaction temperature did not exceed 5° C. After the addition was completed, the reaction mixture was stirred for 2 hours at 10˜15° C. This reaction mixture was filtered, and the filter cake was washed with petroleum ether (2×50 mL). The combined organic layers were evaporated under reduced pressure (30° C.), and the residue was dissolved in petroleum ether (300 mL). The solution was washed with water (100 mL×2) and evaporated, and the residue was dissolved in ethanol (180 mL) at 35° C. with stirring. This solution was cooled to 5˜10° C. and kept for 4 h. The solids were filtered, the filter cake was washed with cold ethanol (0˜5° C., 60 mL) and then dried under vacuum at 25° C. overnight to give 22f as a white solid (72 g, 86.6% yield; HPLC purity 99%, retention time 6.6 min). 1H-NMR (CDCl3, 400 MHz): δ 7.21˜7.28 (m, 3H), 7.06 (d, J=8.0 Hz, 2H), 6.82 (d, J=8.0 Hz, 2H), 4.00 (s, 2H), 1.00 (s, 9H), 0.21 (s, 6H); MS ESI (m/z) 411 [M+1]+, calc. 410.

Workup

  1. customdid not exceed 5° C
  2. additionAfter the addition
  3. filtrationThis reaction mixture was filtered
  4. washthe filter cake was washed with petroleum ether (2×50 mL)
  5. customThe combined organic layers were evaporated under reduced pressure (30° C.)
  6. dissolutionthe residue was dissolved in petroleum ether (300 mL)
  7. washThe solution was washed with water (100 mL×2)
  8. customevaporated
  9. dissolutionthe residue was dissolved in ethanol (180 mL) at 35° C.
  10. stirringwith stirring
  11. temperatureThis solution was cooled to 5˜10° C.
  12. waitkept for 4 h
  13. filtrationThe solids were filtered
  14. washthe filter cake was washed with cold ethanol (0˜5° C., 60 mL)
  15. customdried under vacuum at 25° C. overnight

Sources & evidence

ORD record
ord-d2d062ffaca44173802d77fe11700a3b
Source dataset
uspto-grants-2015_06
Patent number
US09061060B2

Reaction notes

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