Bromine → 11-Benzyl-6-bromo-5-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-triene

HRID 49170Notes

Reaction equation

HRID 49170 reaction equation
[CH2:1]([N:8]1[CH2:19][CH:18]2[CH2:20][CH:10]([CH2:11][C:12]3[CH:13]=[C:14]([O:21][CH3:22])[CH:15]=[CH:16][C:17]=32)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Br:23]Br>C(Cl)Cl.CC(O)=O>[CH2:1]([N:8]1[CH2:19][CH:18]2[CH2:20][CH:10]([CH2:11][C:12]3[C:13]([Br:23])=[C:14]([O:21][CH3:22])[CH:15]=[CH:16][C:17]=32)[CH2:9]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 24408BromineHCID 983905111-Benzyl-5-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-triene

Product 1

HCID 1027059811-Benzyl-6-bromo-5-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trieneYield 28%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

11-Benzyl-5-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-triene (3.00 g, 10.2 mmol) was stirred at 0° C. in CH2Cl2 (10 mL) and AcOH (5 mL) and treated with bromine (3.21 g, 20 mmol) in CH2Cl2 (10 mL) and AcOH (5 mL). After 18 hours the reaction was quenched with 20% aq. NaHSO3 soln. (100 mL). The product was extracted with CH2Cl2 (3×40 mL) and washed with sat. aq. NaHCO3 soln. (3×50 mL). The combined organic layer was dried through a cotton plug, concentrated and chromatographed on Silica gel to provide an oil (1.05 g, 28%). (TLC 30% EtOAc/hexanes Rf 0.48). 1H NMR (CDCl3) δ 7.13 (m, 3H), 6.91 (m, 3H), 6.68 (d, J=8.0 Hz, 1H), 3.90 (s, 3H), 3.36 (s, 2H), 2.86-2.79 (4H), 2.67 (br d, J=9.0 Hz, 1H), 2.31 (br s, 1H), 2.28 (br s, 1H), 2.22 (br s, 1H), 1.78 (AB d, J=13.0 Hz, 2H). GCMS m/e 373, 371 (M+).

Workup

  1. customAfter 18 hours the reaction was quenched with 20% aq. NaHSO3 soln
  2. extractionThe product was extracted with CH2Cl2 (3×40 mL)
  3. washwashed with sat. aq. NaHCO3 soln
  4. customThe combined organic layer was dried through a cotton plug
  5. concentrationconcentrated
  6. customchromatographed on Silica gel

Sources & evidence

ORD record
ord-9760d005e90a4474aba317be4fd50e18
Source dataset
uspto-grants-2004_03
Patent number
US06706702B2

Reaction notes

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