Methylhydrazine → HCID 22379895, compound

HRID 1988769Notes

Reaction equation

HRID 1988769 reaction equation
[Br:1][C:2]1[CH:23]=[CH:22][C:5]2[N:6]([CH2:20][CH3:21])[C:7]([CH2:9][CH2:10][C:11]([C:13]3[CH:18]=[CH:17][CH:16]=[C:15]([F:19])[CH:14]=3)=O)=[N:8][C:4]=2[CH:3]=1.[CH3:24][N:25]([CH:27]([N:31]([CH3:33])C)N(C)C)C.[CH3:34][NH:35]N>>[Br:1][C:2]1[CH:23]=[CH:22][C:5]2[N:6]([CH2:20][CH3:21])[C:7]([CH2:9][C:10]3[C:11]([C:13]4[CH:18]=[CH:17][CH:16]=[C:15]([F:19])[CH:14]=4)=[N:35][N:25]([CH3:27])[CH:24]=3)=[N:8][C:4]=2[CH:3]=1.[Br:1][C:2]1[CH:23]=[CH:22][C:5]2[N:6]([CH2:20][CH3:21])[C:7]([CH2:9][C:10]3[CH:34]=[N:35][N:31]([CH3:33])[C:11]=3[C:13]3[CH:18]=[CH:17][CH:16]=[C:15]([F:19])[CH:14]=3)=[N:8][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 6061MethylhydrazineHCID 79831N,N,N',N',N'',N''-HexamethylmethanetriamineHCID 22379891HCID 22379891, compound

Product 2

HCID 22379895HCID 22379895, compoundHCID 22380303HCID 22380303, compound

Conditions

Temperature
60 °C

Procedure

A mixture of 3-(5-Bromo-1-ethyl-1H-benzoimidazol-2-yl)-1-(3-fluoro-phenyl)-propan-1-one (0.1 g, 0.27 mmol) and tris(dimethylamino)methane (0.077 g, 0.54 mmol) is heated at 60° C. in a sealed tube for 6 hours. The volatile material is removed in vacuo. EtOR (5 mL) and methyl hydrazine (1.1 mmol) are added to the residue. The mixture is heated at 120° C. for 2 hours. The solvent is removed. NaHCO3 (aq.) (10 mL) and DCM (30 mL) are added to the residue. The organic layer is separated and the aqueous layer is extracted with DCM (2×15 mL). The combined organic layers are dried and the solvent removed. The crude is purified by PTLC (ethyl acetate/Hexanes 1:1) to give 5-bromo-1-ethyl-2-[3-(3-fluoro-phenyl)-1-methyl-1H-pyrazol-4-ylmethyl]-1H-benzoimidazole and 5-bromo-1-ethyl-2-[5-(3-fluoro-phenyl)-1-methyl-1H-pyrazol-4-ylmethyl]-1H-benzoimidazole. 5-bromo-1-ethyl-2-[3-(3-fluoro-phenyl)-1-methyl-1H-pyrazol-4-ylmethyl]-1H-benzoimidazole: 1H NMR (CDCl3) δ 7.88 (s, 1H), 7.27-7.42 (m, 4H), 7.00-7.20 (m, 3H), 4.21 (s, 2H), 3.95 (t, 2H), 3.83 (s, 3H), 1.15 (t, 3H). 5-bromo-1-ethyl-2-[5-(3-fluoro-phenyl)-1-methyl-1H-pyrazol-4-ylmethyl]-1H-benzoimidazole: 1H NMR (CDCl3) δ 7.81 (s, 1H), 7.38-7.45 (m, 2H), 7.32 (dd, 1H), 7.00-7.18 (m, 4H), 4.00 (s, 2H), 3.90 (q, 2H), 3.78 (s, 3H), 1.15 (t, 3H).

Workup

  1. customThe volatile material is removed in vacuo
  2. temperatureThe mixture is heated at 120° C. for 2 hours
  3. customThe solvent is removed
  4. additionNaHCO3 (aq.) (10 mL) and DCM (30 mL) are added to the residue
  5. customThe organic layer is separated
  6. extractionthe aqueous layer is extracted with DCM (2×15 mL)
  7. customThe combined organic layers are dried
  8. customthe solvent removed
  9. customThe crude is purified by PTLC (ethyl acetate/Hexanes 1:1)

Sources & evidence

ORD record
ord-a02202e8d2a54079bb497ad35a230f14
Source dataset
uspto-grants-2010_01
Patent number
US07642267B2

Reaction notes

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