Diethylamine → Ethyl 4-(phenylethynyl)benzoate

HRID 533707Notes

Reaction equation

HRID 533707 reaction equation
I[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.[C:13]1([C:19]#[CH:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(NCC)C>CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:13]1([C:19]#[C:20][C:2]2[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 3

HCID 8021DiethylamineHCID 10821PhenylacetyleneHCID 142891Ethyl 4-iodobenzoate

Product 1

HCID 4654671Ethyl 4-(phenylethynyl)benzoateYield 173.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of ethyl 4-iodobenzoate (5.0 g, 18.2 mmol) in DMF (8 mL) was added phenylacetylene (2.25 g, 22.1 mmol), Pd(Ph3P)4 (502 mg, 0.45 mmol), CuI (172 mg, 0.91 mmol) and diethylamine (2 mL). The reaction vessel was sealed and heated at 60° C. for 1 h in a microwave reactor. The reaction was cooled to room temperature, diluted with EtOAc:hexanes (2:1, 150 mL) and washed with water (2×100 mL) and brine (100 mL). The organic phase was dried over MgSO4, filtered and concentrated under vacuum. The crude product was purified by column chromatography (silica gel) using 0 to 10% EtOAc/hexanes to afford ethyl 4-(phenylethynyl)benzoate (7.89 g, 86%) as a pale yellow solid; 1H-nmr (400 MHz, CDCl3) δ 8.05 (d, J=8.0 Hz, 2H), 7.61 (d, J=8.0 Hz, 2H), 7.56 (dd, J=8.0, 2.0 Hz, 2H), 7.41-7.37 (m, 3H), 4.41 (q, J=7.0 Hz, 2H), 1.44 (t, J=7.0 Hz, 3H); LC (275 nM) 5.79 min (>98%); MS (ESI) m/z=250.9.

Workup

  1. customThe reaction vessel was sealed
  2. temperatureThe reaction was cooled to room temperature
  3. washwashed with water (2×100 mL) and brine (100 mL)
  4. dry with materialThe organic phase was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. customThe crude product was purified by column chromatography (silica gel)

Sources & evidence

ORD record
ord-1ba8bfa3729b4e63a255a0029a352fd0
Source dataset
uspto-grants-2014_10
Patent number
US08853392B2

Reaction notes

Loading…