Trifluoroacetic acid → (2-(Tert-butyl-dimethyl-silanyloxy)-ethyl]-(2-iodo-4-nitro-phenyl)-amine

HRID 2037994Notes

Reaction equation

HRID 2037994 reaction equation
[I:1][C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].[Si:12]([O:19][CH2:20][CH:21]=O)([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13].C(O)(C(F)(F)F)=O.[BH3-]C#N.[Na+]>CO>[C:15]([Si:12]([CH3:14])([CH3:13])[O:19][CH2:20][CH2:21][NH:4][C:3]1[CH:5]=[CH:6][C:7]([N+:9]([O-:11])=[O:10])=[CH:8][C:2]=1[I:1])([CH3:18])([CH3:17])[CH3:16]

Participants

6

Reactant 4

HCID 6422Trifluoroacetic acidHCID 2226292-Iodo-4-nitroanilineHCID 41877882-((Tert-butyldimethylsilyl)oxy)acetaldehydeHCID 5003444Sodium cyanoborohydride

Product 1

HCID 59129393(2-(Tert-butyl-dimethyl-silanyloxy)-ethyl]-(2-iodo-4-nitro-phenyl)-amineYield 25%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 2-iodo-4-nitroaniline (2.0 g, 7.6 mmol) and 2-(tert-butyldimethylsilyloxy)-acetaldehyde (3.5 g, 75% purity, 15 mmol) in methanol (30 mL) was added TFA (1.5 mL) at 0° C. The reaction mixture was stirred at this temperature for 30 min before NaCNBH3(900 mg, 15 mmol) was added in portions. The mixture was stirred for 2 h and was then quenched with water. The resulting mixture was extracted with EtOAc (30 mL×3), the combined organic extracts were dried over anhydrous Na2SO4 and evaporated under vacuum, and the residue was purified by chromatography on silica gel (5% ethyl acetate/petroleum) to afford [2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-(2-iodo-4-nitro-phenyl)-amine (800 mg, 25%). 1 H NMR (300 MHz, CDCl3) δ 8.57(d, J=2.7 Hz, 1 H), 8.12(dd, J=2.4 ,9.0 Hz, 1 H), 6.49(d, J=9.3 Hz, 1 H), 5.46(br s, 1 H), 3.89(t, J=5.4 Hz, 2 H), 3.35(q, J=5.4 Hz, 2 H), 0.93(s, 9H), 0.10(s, 6 H).

Workup

  1. additionwas added in portions
  2. customwas then quenched with water
  3. extractionThe resulting mixture was extracted with EtOAc (30 mL×3)
  4. dry with materialthe combined organic extracts were dried over anhydrous Na2SO4
  5. customevaporated under vacuum
  6. customthe residue was purified by chromatography on silica gel (5% ethyl acetate/petroleum)

Sources & evidence

ORD record
ord-4d98cb4d0ec04b1cb20b1f4a55c6549d
Source dataset
uspto-grants-2013_11
Patent number
US08575209B2

Reaction notes

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