Bromine → HCID 53963101, compound

HRID 1077572Notes

Reaction equation

HRID 1077572 reaction equation
[CH2:1]([N:8]1[C@H:17]([CH3:18])[CH2:16][C:15]2[C:10](=[C:11]([O:21][CH3:22])[CH:12]=[C:13]([O:19][CH3:20])[CH:14]=2)[C@H:9]1[CH3:23])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Br:24]Br>C(Cl)Cl>[CH2:1]([N:8]1[C@H:17]([CH3:18])[CH2:16][C:15]2[C:10](=[C:11]([O:21][CH3:22])[CH:12]=[C:13]([O:19][CH3:20])[C:14]=2[Br:24])[C@H:9]1[CH3:23])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 24408BromineHCID 10957910HCID 10957910, compound

Product 1

HCID 53963101HCID 53963101, compoundYield 80.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Into a 25 mL round bottom flask was placed N-benzyl-(1R, 3R)-1,2,3,4-tetrahydro-6,8-dimethoxy-1,3-dimethylisoquinoline (288 mg, 0.9 mmol) dissolved in methylene chloride (3 mL). Bromine (156 mg, 1.0 mmol) in methylene chloride (1 mL ) was added to the solution. The mixture was stirred for 3 h at room temperature and then diluted with methylene chloride (20 mL) and washed with H2O (2×5 ml). The organic layer was dried with sodium sulfate and concentrated in vacuo to yield 360 mg of crude material. Separation on MPLC (hexane/ethyl acetate; 9:1, 3% Et3N) gave N-benzyl-(1R, 3R)-5-bromo-1,2,3,4-tetrahydro-6,8-dimethoxy-1,3-dimethylisoquinoline [106] (282 mg, 78%) as light yellow oil; 1H-NMR (CDCl3, 200 MHz): δ7.31 [m, 5H, Ph], 6.4 [s, Ar-H(7)], 3.97 [q, J=6.6 Hz, CHCH3 ], 3.91 [s, OMe] 3.84, [d, J=14.4 Hz, CHcHdPh], 3.76 [s, OMe], 3.52 [ddq, J=11.6, 6.0, and 4.6 Hz, CH2CHCH3 ], 3.19 [d, J=14.4 Hz, CHcHdPH], 2.74 [dd, J=17.7 and 4.6 Hz, CHaHbCHCH3 ], 2.45 [dd, J=17.7 and 11.6 Hz, CHaHbCHCH3 ], 1.35 [d, J=6.0 Hz, CH2CHCH3 ], and 1.31 [d, J=6.6 Hz, CHCH3 ]; 13C-NMR (CDCl3, 200 MHz): δ157.0, 154.4, 140.9, 136.1, 128.3 [2C], 128.0 [2C], 126.3, 122.1, 104.5, 94.3, 56.3, 55.3 [2C], 51.3, 49.4, 45.7, 33.1, and 19.8; LRMS (EI): m/z 374 (M+ -15, 70), 360, 294, 268, 226, 203, 190, 162, 145 (all <5), 91 (100), 65, and 39.

Workup

  1. customInto a 25 mL round bottom flask was placed
  2. washwashed with H2O (2×5 ml)
  3. dry with materialThe organic layer was dried with sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customto yield 360 mg of crude material
  6. customSeparation on MPLC (hexane/ethyl acetate; 9:1, 3% Et3N)

Sources & evidence

ORD record
ord-75234c29629249ec801c25f20c018c65
Source dataset
uspto-grants-1996_08
Patent number
US05543523

Reaction notes

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