Boron tribromide → HCID 135869734, compound

HRID 885015Notes

Reaction equation

HRID 885015 reaction equation
[Cl:1][C:2]1[CH:29]=[CH:28][C:5]2[NH:6][C:7](=[O:27])[CH:8]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[Cl:26])[N:9]=[C:10]([C:11]3[CH:16]=[CH:15][C:14]([O:17]C)=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1.B(Br)(Br)Br>ClC(Cl)C.ClCCl>[Cl:1][C:2]1[CH:29]=[CH:28][C:5]2[NH:6][C:7](=[O:27])[CH:8]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[Cl:26])[N:9]=[C:10]([C:11]3[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=3)[C:4]=2[CH:3]=1

Participants

5

Reactant 2

HCID 25134Boron tribromide2×HCID 59594390HCID 59594390, compound

Product 1

HCID 135869734HCID 135869734, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 63651,1-DichloroethaneSolvent

Procedure

(Z)-7-Chloro-3-(2-chlorobenzyl)-5-(4-methoxyphenyl)-1H-benzo[e][1,4]diazepin-2(3H)-one (74 mg, 0.174 mmol) was dissolved in dichloroethane (1 mL) under nitrogen and BBr3 (1M in dichloromethane, 0.348 mL, 0.348 mmol) was added dropwise at room temperature (there was an immediate color change from colorless to orange). The reaction mixture was stirred at room temperature for approximately 5 hours. Two more equivalents of BBr3 in dichloromethane were added (0.348 mL, 0.348 mmol) and the mixture was left stirring for another approximately 18 hours. The reaction was carefully quenched with methanol (exothermic) then diluted with dichloromethane and washed twice with water then once with brine (the last wash gelled so some methanol was added to separate the layers). The organic layer was dried (MgSO4). Chromatography eluting with 20-40% ethyl acetate in hexanes gave some starting material plus (Z)-7-chloro-3-(2-chlorobenzyl)-5-(4-hydroxyphenyl)-1H-benzo[e][1,4]diazepin-2(3H)-one as a yellow solid (40 mg, 56%). 1H NMR (300 MHz, CDCl3) δ 3.59-3.89 (m, 3H), 6.30 (br s, 1H), 6.71 (d, J=8 Hz, 2H), 7.09-7.32 (m, 4H), 7.44 (dd, J=9, 2 Hz, 1H), 7.58 (d, J=7 Hz, 1H), 9.13 (s, 1H); ESI m/z 411.0.

Workup

  1. waitthe mixture was left
  2. stirringstirring for another approximately 18 hours
  3. customThe reaction was carefully quenched with methanol (exothermic)
  4. additionthen diluted with dichloromethane
  5. washwashed twice with water
  6. washonce with brine (the last wash
  7. additionwas added
  8. customto separate the layers)
  9. dry with materialThe organic layer was dried (MgSO4)
  10. washChromatography eluting with 20-40% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-34c7d9ad2c194f7796db384be52c7bb2
Source dataset
uspto-grants-2012_08
Patent number
US08242109B2

Reaction notes

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