Boron tribromide → HCID 49850509, compound

HRID 403112Notes

Reaction equation

HRID 403112 reaction equation
C[O:2][C:3]1[CH:35]=[CH:34][CH:33]=[CH:32][C:4]=1[CH2:5][N:6]([CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=1)[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][N:13]1[CH2:18][CH2:17][CH:16]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH2:15][CH2:14]1.B(Br)(Br)Br>C(Cl)Cl>[C:19]1([CH:16]2[CH2:15][CH2:14][N:13]([CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][N:6]([CH2:5][C:4]3[CH:32]=[CH:33][CH:34]=[CH:35][C:3]=3[OH:2])[CH2:25][C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=3)[CH2:18][CH2:17]2)[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 49850482HCID 49850482, compound

Product 1

HCID 49850509HCID 49850509, compoundYield 68.31%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

Compound 3 (0.23 g, 0.4 mmol) was dissolved in 25 mL of CH2Cl2. The solution was cooled at −78° C. in a dry ice CH2Cl2 bath under argon atmosphere for 1 h. After the solution cooled, 1.0 M boron tribromide (3.28 g, 0.013 mol) dissolved in 25 mL of CH2Cl2 was added dropwise. The reaction mixture was allowed to reach room temperature and was stirred overnight. The solvent was removed and quenched with methanol (30 mL×3). After the methanol was removed, hydrochloric saturated methanol (5 mL) was stirred for 1 h at room temperature. The solution was rotovaped and washed with methanol (30 mL×3) before being extracted in CH2Cl2 with water (50 mL×3). The combined organic layers were evaporated and a dissolved in a minimum volume and purified by silica gel TLC plate that was developed in 3% methanolic NH3 (7 M NH3 in methanol)/97% CH2Cl2. The product was obtained as pale yellow oil (68.31%). 1H NMR (CDCl3) δ 8.562 (d, 1H, Ar), 7.652 (ddd, 1H, Ar), 7.280 (m, 3H, Ar), 7.220 (d, 2H, Ar), 7.161 (m, 3H, Ar), 6.980 (d, 1H, Ar), 6.823 (d, 1H, Ar), 6.755 (ddd, 1H, Ar), 3.790 (s, 2H, —CH2—), 3.757 (s, 2H, —CH2—), 3.168 (d, 2H, —CH2—), 2.544 (m, 3H, —CH—CH2—), 2.458 (t, 2H, —CH2—), 2.225 (t, 2H, —CH2—), 2.016 (m, 2H, —CH2—), 1.858 (d, 2H, —CH2—), 1.569 (m, 4H, —CH2—CH2—), 1.236 (m, 4H, —CH2—CH2—). Mass Spec.=458.32 (M+H)+.

Workup

  1. temperatureAfter the solution cooled
  2. additionwas added dropwise
  3. customto reach room temperature
  4. customThe solvent was removed
  5. customquenched with methanol (30 mL×3)
  6. customAfter the methanol was removed
  7. stirringhydrochloric saturated methanol (5 mL) was stirred for 1 h at room temperature
  8. washwashed with methanol (30 mL×3)
  9. extractionbefore being extracted in CH2Cl2 with water (50 mL×3)
  10. customThe combined organic layers were evaporated
  11. dissolutiona dissolved in a minimum volume
  12. custompurified by silica gel TLC plate that

Sources & evidence

ORD record
ord-2ac6d04fcfab406fb37fc5f413005282
Source dataset
uspto-grants-2014_06
Patent number
US08747810B2

Reaction notes

Loading…