Trimethyl orthobeznoate → 1-Benzyl-5-bromo-2-phenyl-1H-benzo[d]imidazole

HRID 2042299Notes

Reaction equation

HRID 2042299 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5](S(O)(=O)=O)=[CH:6][CH:7]=1.O.[CH2:13]([NH:20][C:21]1[C:22]([NH2:28])=[CH:23][C:24]([Br:27])=[CH:25][CH:26]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.COC(OC)(OC)C1C=CC=CC=1>C(Cl)Cl>[CH2:1]([N:20]1[C:21]2[CH:26]=[CH:25][C:24]([Br:27])=[CH:23][C:22]=2[N:28]=[C:13]1[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 69720Trimethyl orthobeznoateHCID 521998p-Toluenesulfonic acid monohydrateHCID 289029062-Benzylamino-5-bromoaniline

Product 1

HCID 591330541-Benzyl-5-bromo-2-phenyl-1H-benzo[d]imidazole

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

p-TsOH.H2O (311.7 mg, 1.606 mmol) was added to a DCM (50 ml) solution of N1-benzyl-4-bromobenzene-1,2-diamine (4451 mg, 16.06 mmol) and trimethyl orthobenzoate (3096 μl, 17.66 mmol) and the resulting mixture was stirred at rt under an atmosphere of Nitrogen for 40 h. The reaction mixture was then concentrated in vacuo to give a yellow solid which was triturated with 40% MeOH/water (375 mL), filtered, washed with saturated NaHCO3 (20 ml)+H2O (80 ml) twice and 40% MeOH/H2O (2×50 ml), and dried to give the title compound. 1H NMR (400 MHz, DMSO-d6) δ ppm=5.44 (s, 2 H), 7.05-7.08 (m, 3 H), 7.30-7.36 (m, 4 H), 7.44-7.50 (m, 3 H), 7.66-7.68 (m, 2 H) and 7.99 (dd, 1 H, J=0.4 & 1.6 Hz). MS (ES+): m/z 363.20 and 365.26 [MH+].

Workup

  1. concentrationThe reaction mixture was then concentrated in vacuo
  2. customto give a yellow solid which
  3. customwas triturated with 40% MeOH/water (375 mL)
  4. filtrationfiltered
  5. washwashed with saturated NaHCO3 (20 ml)+H2O (80 ml) twice
  6. dry with material40% MeOH/H2O (2×50 ml), and dried

Sources & evidence

ORD record
ord-079c1d24178e4c349a2ffcb5c0095285
Source dataset
uspto-grants-2013_11
Patent number
US08586546B2

Reaction notes

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