2-Iodo-4-nitroaniline → HCID 53741589, compound

HRID 1769636Notes

Reaction equation

HRID 1769636 reaction equation
I[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].[CH3:12][Si:13]([CH3:27])([CH3:26])[C:14]#[C:15][CH2:16][CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20].C([O-])(=O)C.[K+].[Cl-].[Li+]>CN(C=O)C.CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N+:9]([C:7]1[CH:8]=[C:2]2[C:3](=[CH:5][CH:6]=1)[NH:4][C:14]([Si:13]([CH3:12])([CH3:27])[CH3:26])=[C:15]2[CH2:16][CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:20])[CH3:21])([O-:11])=[O:10]

Participants

8

Reactant 4

HCID 2226292-Iodo-4-nitroanilineHCID 433294Lithium ChlorideHCID 517044Potassium AcetateHCID 13679439tert-Butyl(dimethyl){[4-(trimethylsilyl)but-3-yn-1-yl]oxy}silane

Product 1

HCID 53741589HCID 53741589, compoundYield 42.4%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 2-iodo-4-nitroaniline (7.92 g, 0.030 mol), 1-(trimethylsilyl)-4-(t-butyldimethylsiloxy)-1-butyne (15.36 g, 0.060 mol), potassium acetate (14.70 g, 0.15 mol), lithium chloride (1.27 g, 0.030 mol) and palladium (II) acetate (0.675 g, 0.003 mol) in 100 mL of dry DMF was heated at 70° C. (oil-bath temperature) under Ar for 2.5 h. The cooled reaction mixture was diluted with ether and the aqueous phase was separated and extracted with ethyl acetate. The combined organic phases were washed (H2O, brine), dried (Na2SO4) and evaporated. The resulting residue was chromatographed (SiO2 /hexane-ethyl acetate, 4:1) to give a dark orange solid which was rechromatographed (SiO2 /hexane-CH2Cl2, 4:1 to 6:4) to give the title compound (5.00 g, 42%) as a yellow solid: IR (neat) 3414, 1328, 1253, 845 cm-1 ; 1H NMR (CDCl3, 200 MHz) δ 8.63 (d, J=2.2 Hz, 1H), 8.21 (br s, 1H), 8.09 (dd, J=9.0, 2.2 Hz, 1H), 7.35 (d, J=9.0 Hz, 1H), 3.84 (t, J=7.2 Hz, 2H), 3.09 (t, J=7.2 Hz, 2H), 0.85 (s, 9H), 0.42 (s, 9H), -0.01 (s, 6H).

Workup

  1. customThe cooled reaction mixture
  2. customthe aqueous phase was separated
  3. extractionextracted with ethyl acetate
  4. washThe combined organic phases were washed (H2O, brine)
  5. dry with materialdried (Na2SO4)
  6. customevaporated
  7. customThe resulting residue was chromatographed (SiO2 /hexane-ethyl acetate, 4:1)
  8. customto give a dark orange solid which
  9. customwas rechromatographed (SiO2 /hexane-CH2Cl2, 4:1 to 6:4)

Sources & evidence

ORD record
ord-46cbe4e017f2451bbba70f566988022a
Source dataset
uspto-grants-1995_01
Patent number
US05382592

Reaction notes

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