3,4-dihydro-2H-pyran → 2H-Pyran, 2-(9-decynyloxy)tetrahydro-

HRID 1523005Notes

Reaction equation

HRID 1523005 reaction equation
[CH2:1]([OH:11])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]#[CH:10].[O:12]1[CH:17]=[CH:16][CH2:15][CH2:14][CH2:13]1.CC1C=CC(S([O-])(=O)=O)=CC=1.C1C=C[NH+]=CC=1>C(Cl)Cl>[O:12]1[CH2:17][CH2:16][CH2:15][CH2:14][CH:13]1[O:11][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]#[CH:10]

Participants

5

Reactant 3

HCID 80803,4-dihydro-2H-pyranHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 5437529-Decyn-1-ol

Product 1

HCID 109116082H-Pyran, 2-(9-decynyloxy)tetrahydro-Yield 98%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a flame-dried round-bottomed flask was added 9-decyn-1-ol (1 equiv, 32.4 mmol, 5.00 g), dihydropyran (1.5 equiv, 48.6 mmol, 4.09 g, 4.5 mL), CH2Cl2 (50 mL), and PPTS (0.1 equiv, 3.24 mmol, 800 mg). The reaction was stirred for 16 h at rt and quenched with sat. aq. NaHCO3 (40 mL). The layers were separated and the aqueous layer was extracted with CH2Cl2 (2×20 mL). The combined organic layers were washed with H2O (30 mL), dried with Na2SO4, concentrated in vacuo, and purified by flash column chromatography (5% EtOAc/Hex) to afford 9-Decyn-1-ol tetrahydropyranyl ether (7.55 g, 31.7 mmol, 98%). TLC Rf=0.30 (5% EtOAc/Hex); 1HNMR (600 MHz): δ 4.55-4.62 (1H), 3.83-3.91 (m, 1H), 3.70-3.78 (m, 1H), 3.48-3.55 (m, 1H), 3.36-3.43 (m, 1H), 2.19 (td, 2H, J1=7.1 Hz, J2=2.6 Hz), 1.95 (t, 1H, J=2.6), 1.80-1.89 (1H), 1.69-1.76 (1H), 1.50-1.63 (8H), 1.28-1.44 (8H); 13CNMR (150 MHz): δ 98.8, 84.7, 68.1, 67.6, 62.3, 30.8, 29.7, 29.3, 29.0, 28.7, 28.5, 26.2, 25.5, 19.7, 18.4.

Workup

  1. customquenched with sat. aq. NaHCO3 (40 mL)
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with CH2Cl2 (2×20 mL)
  4. washThe combined organic layers were washed with H2O (30 mL)
  5. dry with materialdried with Na2SO4
  6. concentrationconcentrated in vacuo
  7. custompurified by flash column chromatography (5% EtOAc/Hex)

Sources & evidence

ORD record
ord-739b47108914474d9b32652f0c894637
Source dataset
uspto-grants-2015_07
Patent number
US09079835B2

Reaction notes

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