Diethylamine → HCID 86749181, compound

HRID 2260879Notes

Reaction equation

HRID 2260879 reaction equation
C[Si](C)(C)[C:3]#[C:4][C:5]#[C:6][CH3:7].CCCC[N+](CCCC)(CCCC)CCCC.[F-].[CH2:28]([S:35]/[C:36](/I)=[CH:37]\[CH:38]=[C:39](/[S:46][CH2:47][C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1)\[C:40]#[C:41][Si:42]([CH3:45])([CH3:44])[CH3:43])[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.N(CC)CC>O.C1C=CC=CC=1.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.CN(C=O)C>[CH2:47]([S:46]/[C:39](=[CH:38]\[CH:37]=[C:36](/[S:35][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)\[C:3]#[C:4][C:5]#[C:6][CH3:7])/[C:40]#[C:41][Si:42]([CH3:45])([CH3:44])[CH3:43])[C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1

Participants

10

Reactant 4

HCID 8021DiethylamineHCID 2724141Tetrabutylammonium FluorideHCID 10964580HCID 10964580, compoundHCID 86749182HCID 86749182, compound

Product 1

HCID 86749181HCID 86749181, compoundYield 57%

Reagents, catalysts & solvents 5

HCID 962WaterCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 241BenzeneSolventHCID 6228DimethylformamideSolvent

Procedure

To a DMF (5 mL) solution of 1-trimethylsilyl-1,3-pentadiyne (0.4 g, 2.94 mmol) under argon was added TBAF (0.8 g, 3 mmol) and several drops of water. The dark brown solution was stirred for 2 h at room temperature, then diluted with benzene (3 mL). The benzene layer was washed with saturated brine (5×5 mL). After drying (MgSO4) and filtering, the solution was transferred to a flask containing 8 (500 mg, 0.96 mmol), (Ph3P)2PdCl2 (34 mg, 0.048 mmol), CuI (9 mg, 0.048 mmol) and Et2NH (1 mL). The mixture was stirred under argon at room temperature for 40 h, and then concentrated in vacuo. Ether (100 mL) and water (25 mL) were added, the layers were separated, the ether layer was washed with brine (3×20 mL), dried (MgSO4), concentrated in vacuo and the residue purified by flash column chromatography (1:6 CH2Cl2 :hexanes) giving 9 as a yellow oil (0.25 g, 57% yield): 1H NMR δ 7.15-7.3 (m, 10 H), 6.99 (d, J=11.7 Hz, 1 H), 6.90 (d, J=11.7 Hz, 1 H), 4.09 (s, 2 H), 4.06 (s, 2 H), 1.98 (s, 3 H), 0.20 (s, 9 H); 13C NMR δ 120-138 (several), 102.32 102.09, 84.37, 80.86, 72.45, 64.35, 37.36, 37.27, 4.82, -0.200.

Workup

  1. washThe benzene layer was washed with saturated brine (5×5 mL)
  2. dry with materialAfter drying (MgSO4)
  3. filtrationfiltering
  4. customthe solution was transferred to a flask
  5. stirringThe mixture was stirred under argon at room temperature for 40 h
  6. concentrationconcentrated in vacuo
  7. additionEther (100 mL) and water (25 mL) were added
  8. customthe layers were separated
  9. washthe ether layer was washed with brine (3×20 mL)
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated in vacuo
  12. customthe residue purified by flash column chromatography (1:6 CH2Cl2 :hexanes)

Sources & evidence

ORD record
ord-20fa26698d5d4e7daf2fc51ec6de1e2f
Source dataset
uspto-grants-1995_12
Patent number
US05478959

Reaction notes

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