tert-BUTYL CHLORIDE → HCID 67127354, compound

HRID 451243Notes

Reaction equation

HRID 451243 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][CH:8]=[C:9]2[O:12][Si](C)(C)C)=[CH:4][CH:3]=1.Cl[C:18]([CH3:21])([CH3:20])[CH3:19]>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][CH:8]([C:18]([CH3:21])([CH3:20])[CH3:19])[C:9]2=[O:12])=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 10486tert-BUTYL CHLORIDEHCID 11323959HCID 11323959, compound

Product 1

HCID 67127354HCID 67127354, compoundYield 100.8%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-40 °C

Procedure

step a—A solution of (7-bromo-3,4-dihydronaphthalen-1-yloxy)trimethylsilane (6.85 g, 11.5 mmol, CASRN 309929-09-7) and DCM (23.0 mL) was cooled to −40° C. 2-Chloro-2-methylpropane (1.12 g, 1.32 mL, 12.1 mmol) was added and the solution stirred under nitrogen. A solution of TiCl4 (2.19 g, 1.27 mL, 11.5 mmol) in DCM (6 mL) was added dropwise while maintaining the solution at −40° C. Soon after addition was complete TLC indicated ca. 50% conversion. The reaction was stirred at RT over the weekend then poured onto ice. The mixture was partitioned between EtOAc and H2O and aqueous layer was neutralized with satd. aq. NaHCO3. The mixture was filtered through a plug of celite to a remove chunky white precipitate. The organic layer was separated, washed with brine, dried (MgSO4), filtered and concentrated. The crude product was applied to a hexane equilibrated SiO2 column and eluted with an EtOAc/hexane gradient (0 to 5% EtOAc) to afford 3.26 g (quantitative) of 7-bromo-2-tert-butyl-3,4-dihydro-2H-naphthalen-1-one (109) a yellow solid.

Workup

  1. additionSoon after addition
  2. stirringThe reaction was stirred at RT over the weekend
  3. additionthen poured onto ice
  4. customThe mixture was partitioned between EtOAc and H2O and aqueous layer
  5. filtrationThe mixture was filtered through a plug of celite to a remove chunky white precipitate
  6. customThe organic layer was separated
  7. washwashed with brine
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. washeluted with an EtOAc/hexane gradient (0 to 5% EtOAc)

Sources & evidence

ORD record
ord-73a1c21210854294945d33eebaf1a096
Source dataset
uspto-grants-2013_07
Patent number
US08487103B2

Reaction notes

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