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

HRID 1244418Notes

Reaction equation

HRID 1244418 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 (300 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 soin. (100 mL). The produce was extracted with CH2Cl2 (3×40 mL) and washed with sat. aq. NaHCO3 soin. (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), 2.88-2.79 (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 soin
  2. extractionThe produce was extracted with CH2Cl2 (3×40 mL)
  3. washwashed with sat. aq. NaHCO3 soin
  4. customThe combined organic layer was dried through a cotton plug
  5. concentrationconcentrated
  6. customchromatographed on Silica gel

Sources & evidence

ORD record
ord-ca0769b5a71448c48c3b0827764b48f4
Source dataset
uspto-grants-2006_10
Patent number
US07122534B2

Reaction notes

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