HCID 90349596, compound → HCID 102447499, compound

HRID 928880Notes

Reaction equation

HRID 928880 reaction equation
I[C:2]1[CH:17]=[CH:16][C:5]([C:6]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])=[O:7])=[CH:4][CH:3]=1.[C:18]([C:20]1[CH:35]=[CH:34][C:23]([C:24]([O:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])=[O:25])=[CH:22][CH:21]=1)#[CH:19]>C(N(CC)CC)C.O1CCCC1.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:9]([O:8][C:6]([C:5]1[CH:16]=[CH:17][C:2]([C:19]#[C:18][C:20]2[CH:35]=[CH:34][C:23]([C:24]([O:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])=[O:25])=[CH:22][CH:21]=2)=[CH:3][CH:4]=1)=[O:7])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

8

Reactant 2

HCID 90349596HCID 90349596, compoundHCID 118588387HCID 118588387, compound

Product 1

HCID 102447499HCID 102447499, compoundYield 95.5%

Reagents, catalysts & solvents 5

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8471TriethylamineSolvent

Procedure

Under a nitrogen atmosphere, heptyl 4-iodobenzoate (2a) (3.64 g, 10.5 mmol) was dissolved in anhydrous triethylamine (8.6 mL), and anhydrous tetrahydrofuran (4.0 mL), triphenylphosphine (39.3 mg, 0.150 mmol), copper (I) iodide (43.8 mg, 0.230 mmol), and Pd(PPh3)2Cl2 (27.9 mg, 0.0397 mmol) were added. Thereafter, a solution of heptyl 4-ethynylbenzoate (4a) (2.64 g, 10.8 mmol) in anhydrous tetrahydrofuran (2.0 mL) was slowly added dropwise, and the mixture was stirred at room temperature for 3 hr. The reaction solution was filtered through celite and, after removal under reduced pressure, diluted with ethyl acetate, washed with water and saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography (ethyl acetate:hexane=1:10). Subsequent recrystallization from methanol/ethanol (5:1, v/v) gave bis[4-(heptyloxycarbonyl)phenyl]acetylene (5a) (4.64 g, yield 95%) as a white solid.

Workup

  1. filtrationThe reaction solution was filtered through celite
  2. customafter removal under reduced pressure
  3. additiondiluted with ethyl acetate
  4. washwashed with water and saturated brine
  5. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was purified by column chromatography (ethyl acetate:hexane=1:10)
  8. customSubsequent recrystallization from methanol/ethanol (5:1

Sources & evidence

ORD record
ord-b56fd436add940f7a05b599f08ca4b13
Source dataset
uspto-grants-2016_03
Patent number
US09290592B2

Reaction notes

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