Triethylamine → HCID 23436447, compound

HRID 2121264Notes

Reaction equation

HRID 2121264 reaction equation
Br[C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[C:15]([C:19]#[CH:20])([CH3:18])([CH3:17])[CH3:16].C(N(CC)CC)C>C(OCC)(=O)C.[Cu](I)I>[CH3:16][C:15]([CH3:18])([CH3:17])[C:19]#[C:20][C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 135123,3-Dimethyl-1-butyne2×HCID 15833211Methyl 2-Bromo-4-nitrobenzoate

Product 1

HCID 23436447HCID 23436447, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Methyl 2-bromo-4-nitrobenzoate (2.0 g, 7.7 mmol) and t-butylacetylene (0.70 g, 8.5 mmol) were dissolved into 50 mLs. of dry triethylamine to which 2 mole % of copper iodide (0.029 g, 0.15 mmol) and 5 mole. % of tetrakis(triphenylphosine)palladium(0) (0.45 g, 0.38 mmol) were added. The reaction was stirred at 400° C. for 16 hours before an additional ½ equivalent of t-butylacetylene was added. The reaction continued for an additional 24 hours at which time the reaction was completed as determined by TLC. The reaction mixture was taken up in ethyl acetate, washed with distilled water and the organic layer dried over magnesium sulfate. After concentrating, the residue was purified by chromatography (1:9 ethyl acetate/hexanes ) to give the title compound (1.7 g, 85%) as a white solid. m.p. 88-89° C.; 1H NMR (300 MHz, CDCl3) δ 8.30 (d, J=2.2 Hz, 1H, Aromatic), 8.10 (dd, J=2.3, 8.6 Hz, 1H, Aromatic), 7.99 (d, J=8.7 Hz, 1H, Aromatic), 3.99 (s, 3H, OCH3), 1.35 (s, 9H, t-Butyl); 13C NMR (75 MHz, CDCl3) δ 165.9, 149.4, 137.7, 131.4, 128.7, 126.2, 121.8, 107.1, 76.5, 52.8, 30.8, 28.6; MS m/e calc'd 261.1001, found 261.1007.

Workup

  1. additionwas added
  2. washwashed with distilled water
  3. dry with materialthe organic layer dried over magnesium sulfate
  4. concentrationAfter concentrating
  5. customthe residue was purified by chromatography (1:9 ethyl acetate/hexanes )

Sources & evidence

ORD record
ord-2d7ab10b265044d9954f69ee394aef8d
Source dataset
uspto-grants-2004_02
Patent number
US06693123B2

Reaction notes

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