Triethylamine → 3-Amino-2-(4-chloro-phenylethynyl)-benzoic acid methyl ester

HRID 489557

Reaction equation

HRID 489557 reaction equation
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-])=O)[C:5]=1I.[Cl:15][C:16]1[CH:21]=[CH:20][C:19]([C:22]#[CH:23])=[CH:18][CH:17]=1.C(N(CC)CC)C>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].[Cu]I>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([NH2:10])[C:5]=1[C:23]#[C:22][C:19]1[CH:20]=[CH:21][C:16]([Cl:15])=[CH:17][CH:18]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 70118Benzene, 1-chloro-4-ethynyl-HCID 264093Methyl 2-iodo-3-nitrobenzoate

Product 1

HCID 183400043-Amino-2-(4-chloro-phenylethynyl)-benzoic acid methyl ester

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

2-iodo-3-nitro-benzoic acid methyl ester (0.79 g, 2.84 mmol), 1-chloro-4-ethynylbenzene (0.41 g, 2.99 mmol), palladium tetrakis(triphenylphosphine) (0.16 g, 0.14 mmol), copper (I) iodide (0.03 g, 0.14 mmol), and triethylamine (1.44 g, 14.19 mmol) were dissolved in 15 mL toluene. Argon was bubbled through the resulting solution for 15 min. The reaction was stirred under argon at 80° C. for 2 h and 20 min. The reaction mixture was then washed once with water, dried (MgSO4), and concentrated in vacuo. The orange oil was purified by flash chromatography eluting with 50 to 100% CHCl3/hexanes to yield 3-amino-2-(4-chloro-phenylethynyl)-benzoic acid methyl ester, 0.76 g (94%) as a yellow oil. 1H NMR (300 MHz, d6-DMSO) δ 3.84 (s, 3H), 5.84 (br s, 2H), 6.97 (dd, J=8.1, 1.3 Hz, 1H), 7.05 (dd, J=7.5, 1.2 Hz, 1H), 7.17 (app t, J=7.5 Hz, 1H), 7.49 (d, J=8.7 Hz, 2H), 7.63 (d, J=8.7 Hz, 2H). MS (electrospray, MH+) 286.

Workup

  1. customArgon was bubbled through the resulting solution for 15 min
  2. washThe reaction mixture was then washed once with water
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customThe orange oil was purified by flash chromatography
  6. washeluting with 50 to 100% CHCl3/hexanes

Sources & evidence

ORD record
ord-d6494735342649c79e2341aaf772efbf
Source dataset
uspto-grants-2005_12
Patent number
US06977298B2

Linked notes

Loading…