Chlorotrimethylsilane → 1-(2,2-Dimethoxyethyl)-2,3-dinitrobenzene

HRID 730567Notes

Reaction equation

HRID 730567 reaction equation
[N+:1]([C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[CH:6][C:5]=1[CH3:13])([O-:3])=[O:2].[CH3:14][O:15][CH:16]([O:20][CH3:21])N(C)C.Cl[Si](C)(C)C>CN(C=O)C.CO>[CH3:14][O:15][CH:16]([O:20][CH3:21])[CH2:13][C:5]1[CH:6]=[CH:7][CH:8]=[C:9]([N+:10]([O-:12])=[O:11])[C:4]=1[N+:1]([O-:3])=[O:2]

Participants

6

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 117612,3-DinitrotolueneHCID 78373Dimethylformamide dimethyl acetal

Product 1

HCID 578349721-(2,2-Dimethoxyethyl)-2,3-dinitrobenzeneYield 44%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 2,3-dinitrotoluene (3.02 g, 16.6 mmol) in 25 mL of DMF was added dimethylformamide dimethylacetal (6.0 mL, 5.4 g, 45 mmol), and the solution was brought to 140° C. and stirred for 16 hours. The solvent was removed under reduced pressure to afford a dark red solid mass. This crude enamine was dissolved in 40 mL of MeOH and 4.0 mL of chlorotrimethylsilane (3.4 g, 31.7 mmol) was added. The solution was brought to reflux and stirred for 16 hours at reflux. The solvent was removed under reduced pressure and the crude material chromatographed directly to afford the 1-(2,2-dimethoxy-ethyl)-2,3-dinitro-benzene (1.85 g, 44%). 1H NMR (CDCl3) δ 2.96 (2H, d, J=5.2 Hz), 3.35 (6H, s), 4.49 (1H, t, J=5.2 Hz), 7.60 (apparent t, 1H, J=8.0 Hz), 7.76 (d, 1H, J=6.5 Hz), 8.05 (dd, 1H, J=1.3, 8.0).

Workup

  1. customwas brought to 140° C.
  2. customThe solvent was removed under reduced pressure
  3. customto afford a dark red solid mass
  4. temperatureto reflux
  5. stirringstirred for 16 hours
  6. temperatureat reflux
  7. customThe solvent was removed under reduced pressure
  8. customthe crude material chromatographed directly

Sources & evidence

ORD record
ord-2f28332e14814695bc9bdfb6228cb6b9
Source dataset
uspto-grants-2009_09
Patent number
US07582760B2

Reaction notes

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