Chloroform → HCID 19815311, compound

HRID 653864Notes

Reaction equation

HRID 653864 reaction equation
S(Cl)(Cl)=O.[CH2:5]([C:9]1[N:10]([CH2:17][C:18]2[CH:23]=[CH:22][C:21]([C:24]#[N:25])=[CH:20][CH:19]=2)[C:11]([CH2:15]O)=[C:12]([Cl:14])[N:13]=1)[CH2:6][CH2:7][CH3:8].C(Cl)(Cl)Cl.[C-:30]#[N:31].[Na+]>CS(C)=O.O>[CH2:5]([C:9]1[N:10]([CH2:17][C:18]2[CH:23]=[CH:22][C:21]([C:24]#[N:25])=[CH:20][CH:19]=2)[C:11]([CH2:15][C:30]#[N:31])=[C:12]([Cl:14])[N:13]=1)[CH2:6][CH2:7][CH3:8]

Participants

7

Reactant 4

HCID 6212ChloroformHCID 8929Sodium CyanideHCID 24386Thionyl ChlorideHCID 19815325HCID 19815325, compound

Product 1

HCID 19815311HCID 19815311, compoundYield 52.3%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Procedure

Thionyl chloride (3.60 mL, 49 mmol, 5 eq) was slowly dripped into a solution of 2-butyl-4-chloro-1-(4-cyanobenzyl)-5-hydroxymethylimidazole (3.0 g, 9.9 mmol, 1 eq) in a minimum of CHCl3. The mixture was stirred for 2 hours at room temperature after which the solvent was removed in vacuo and the residue suspended in toluene (200 mL). The toluene was removed on the rotary evaporator and this procedure was repeated again to remove all traces of thionyl chloride. The chloride was then dissolved in DMSO (minimum to dissolve) and added to a solution of sodium cyanide (2.90 g, 59 mmol, 6 eq) in DMSO (200 ml). The solution was stirred overnight under N2 at room temperature after which 500 mL H2O was added and the aqueous layer was extracted three times with 300 mL of ethyl acetate. The organic layers were dried and concentrated and the residue flash chromatographed in 4:1 hexane/ethyl acetate over silica gel to give 1.62 g of a light yellow solid; m.p. 109.5°-113.0° NMR (200 MHz, CDCl3) δ 7.70 (d, 2H, J=10Hz); 7.12 (d, 2H, J=10Hz); 3.51 (s, 2H); 2.60 (t, 2H, J=7Hz); 1.70 (m, 2H); 1.40 (m, 2H); 0.90 (t, 3H, J=7Hz). Mass spectrum shows M+ =312/314. Mass Calcd. for C17H17ClN4 : 312.1139, Found 312.1126.

Workup

  1. customwas removed in vacuo
  2. customThe toluene was removed on the rotary evaporator
  3. customto remove all traces of thionyl chloride
  4. dissolutionThe chloride was then dissolved in DMSO (minimum to dissolve)
  5. additionwas added
  6. extractionthe aqueous layer was extracted three times with 300 mL of ethyl acetate
  7. customThe organic layers were dried
  8. concentrationconcentrated
  9. customthe residue flash chromatographed in 4:1 hexane/ethyl acetate over silica gel

Sources & evidence

ORD record
ord-35dcc4f9e89d40bf8eeacc0b5133ccc3
Source dataset
uspto-grants-1992_07
Patent number
US05128355

Reaction notes

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