Methyl morpholine oxide → 3-(1-Naphthalenyl)-2-propynal

HRID 1096725Notes

Reaction equation

HRID 1096725 reaction equation
[C:1]1([C:11]#[C:12][CH2:13][OH:14])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.C[N+]1([O-])CCOCC1>ClCCl.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[C:1]1([C:11]#[C:12][CH:13]=[O:14])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 2

HCID 82029Methyl morpholine oxideHCID 114011513-(1-Naphthyl)-2-propyn-1-ol

Product 1

HCID 112408133-(1-Naphthalenyl)-2-propynalYield 82.1%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 3-naphthalen-1-yl-prop-2-yn-1-ol (3.51 g, 19.26 mmol) in dichloromethane (60 mL) and tetrapropylammonium perruthenate (0.14 g, 0.39 mmol, 2 mol %) was stirred at 0° C. under an atmosphere of nitrogen. N-methylmorpholin-N-oxide (4.06 g, 34.67 mmol, 1.8 eq.) was divided into 4 portions and the first portion (1.01 g, 8.67 mmol) was added to the reaction mixture and the resulting black mixture was stirred at room temperature for an hour. The remaining portions were added sequentially at hourly intervals and the mixture was left to stir for a further 19 hours. The TLC of the reaction mixture indicated that the starting material had been consumed and the reaction was quenched by the addition of saturated aqueous sodium bicarbonate (50 mL) and the reaction mixture was extracted with dichloromethane (3×50 mL), dried over sodium sulphate and concentrated in vacuo to afford a black residue. The crude material was purified by flash chromatography (SiO2, ethyl acetate:petroleum ether 40-60; 30%:70%) to afford the desired compound as a yellow oil (2.85 g, 82%). 1H NMR (400 MHz, CDCl3) δ ppm 7.49-7.65 (4H, m, ArH), 7.89 (1H, d, J 8.0 Hz, ArH), 7.99-8.01 (1H, d, J 8.0 Hz, ArH), 8.32-8.34 (1H, d, J 8.4 Hz, ArH), 9.57 (1H, s, CHO).

Workup

  1. additionthe first portion (1.01 g, 8.67 mmol) was added to the reaction mixture
  2. additionThe remaining portions were added sequentially at hourly intervals
  3. waitthe mixture was left
  4. stirringto stir for a further 19 hours
  5. customhad been consumed
  6. customthe reaction was quenched by the addition of saturated aqueous sodium bicarbonate (50 mL)
  7. extractionthe reaction mixture was extracted with dichloromethane (3×50 mL)
  8. dry with materialdried over sodium sulphate
  9. concentrationconcentrated in vacuo
  10. customto afford a black residue
  11. customThe crude material was purified by flash chromatography (SiO2, ethyl acetate:petroleum ether 40-60; 30%:70%)

Sources & evidence

ORD record
ord-3ffba07b0c624bf7b5c8c1b046441365
Source dataset
uspto-grants-2012_03
Patent number
US08138377B2

Reaction notes

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