Trimethylsilylacetylene → HCID 86719903, compound

HRID 1748940Notes

Reaction equation

HRID 1748940 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].Br[CH:8]1[C:13]([Cl:14])=[C:12]([CH2:15][CH3:16])[C:11](Br)=[C:10]([Cl:18])[C:9]1([O:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[CH2:19][CH3:20]>C(NC(C)C)(C)C.C1(C)C=CC=CC=1.O.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.[Cu]I>[Cl:18][CH:10]1[C:11]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])=[C:12]([CH2:15][CH3:16])[C:13]([Cl:14])=[C:8]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[C:9]1([O:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[CH2:19][CH3:20]

Participants

8

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 86719904HCID 86719904, compound

Product 1

HCID 86719903HCID 86719903, compoundYield 53.5%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 7912DiisopropylamineSolvent

Procedure

Trimethylsilylacetylene (3.1 mL, 21.43 mmol), PdCl2(PPh3)2 (400 mg, 0.6 mmol), and CuI (235 mg, 0.79 mmol) were added successively to a deaerated solution of 2,5-dibromo-3,6-dichloro-1,4-diethylhexyloxybenzene (10) (4.00 g, 7.14 mmol) in diisopropylamine (25 mL) and toluene (55 mL). The resulting mixture was refluxed for 48 hours, then diluted with water (150 mL), and extracted with hexane (2×80 mL). The extract was washed with water (2×80 mL) and dried (MgSO4). Evaporation of the solvent gave an oily residue, which was purified by column chromatography (hexane:CH2Cl2, 98:2) to give an orange-red solid (1.90 gm, 45%). 1H-NMR(CDCl3): δ 3.87 (m, 4H), 1.81 (m, 2H), 1.31-1.64 (m, 12H), 0.97 (t, J=7.5 Hz, 6H), 0.92 (t, J=7.5 Hz, 6H). MS (EI): Calculated. 595.8. found [M+I]+, 596.8.

Workup

  1. temperatureThe resulting mixture was refluxed for 48 hours
  2. extractionextracted with hexane (2×80 mL)
  3. washThe extract was washed with water (2×80 mL)
  4. dry with materialdried (MgSO4)
  5. customEvaporation of the solvent
  6. customgave an oily residue, which
  7. customwas purified by column chromatography (hexane:CH2Cl2, 98:2)

Sources & evidence

ORD record
ord-48ad068792474f268e5797ee3bdd112c
Source dataset
uspto-grants-2015_10
Patent number
US09153785B2

Reaction notes

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