N-bromobutanimide → 2-bromo-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole-4-carbonitrile

HRID 1992019Notes

Reaction equation

HRID 1992019 reaction equation
[CH3:1][Si:2]([CH3:15])([CH3:14])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[CH:11]=[C:10]([C:12]#[N:13])[N:9]=[CH:8]1.C[Si](C)(C)CCOCN1C(C#N)=CN=C1.[Br:31]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[Br:31][C:8]1[N:7]([CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:15])([CH3:14])[CH3:1])[CH:11]=[C:10]([C:12]#[N:13])[N:9]=1

Participants

5

Reactant 3

HCID 67184N-bromobutanimideHCID 584311371-(2-trimethylsilanyl-ethoxymethyl)-1H-imidazole-4-carbonitrileHCID 59128552HCID 59128552, compound

Product 1

HCID 579205782-bromo-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole-4-carbonitrile

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
60 °C

Procedure

A 22-L, four-neck, round-bottom flask equipped with a mechanical stirrer, a temperature probe, and a condenser with a nitrogen inlet was charged with a mixture of 1-(2-trimethylsilanyl-ethoxymethyl)-1H-imidazole-4-carbonitrile and 3-(2-trimethylsilanyl-ethoxymethyl)-3H-imidazole-4-carbonitrile [600 g, 2.69 mol, as prepared in the previous step) and carbon tetrachloride (1.8 L). Agitation was initiated and the mixture was heated to 60° C. At this point N-bromosuccinimide (502 g, 2.82 mol) was added in several portions over 30 min, which resulted in an exotherm to 74° C. The reaction was allowed to cool to 60° C. and further stirred at 60° C. for 1 h. The reaction was allowed to cool slowly to ambient temperature and the resulting slurry was filtered and the filtrate washed with satd NaHCO3 solution (4.0 L). The organics were passed through a plug of silica gel (8×15 cm, silica gel; 600 g) using 2:1 heptane/ethyl acetate (6.0 L) as eluent. The fractions containing the product (based on TLC analysis) were combined and concentrated under reduced pressure to give a crystalline light yellow solid, which was then filtered and washed with heptane (500 mL) to give the title compound as a crystalline white solid [593 g, 73%). The 1H and 13C NMR spectra were consistent with the assigned structure and showed no evidence of the minor regioisomer.

Workup

  1. customwhich resulted in an exotherm to 74° C
  2. temperatureto cool to 60° C.
  3. temperatureto cool slowly to ambient temperature
  4. filtrationthe resulting slurry was filtered
  5. washthe filtrate washed with satd NaHCO3 solution (4.0 L)
  6. additionThe fractions containing the product (based on TLC analysis)
  7. concentrationconcentrated under reduced pressure
  8. customto give a crystalline light yellow solid, which
  9. filtrationwas then filtered
  10. washwashed with heptane (500 mL)

Sources & evidence

ORD record
ord-dc4be569758f43ad9df8b3f9869e385d
Source dataset
uspto-grants-2010_01
Patent number
US07645755B2

Reaction notes

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