3,4-dihydro-2H-pyran → N-ethyl-N-[6-(tetrahydropyran-2-yl)oxyhexyl]-4-bromoaniline

HRID 1004777Notes

Reaction equation

HRID 1004777 reaction equation
[CH2:1]([N:3]([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][OH:17])[C:4]1[CH:9]=[CH:8][C:7]([Br:10])=[CH:6][CH:5]=1)[CH3:2].[O:18]1[CH:23]=[CH:22][CH2:21][CH2:20][CH2:19]1.O.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.C(=O)([O-])O.[Na+]>C(Cl)(Cl)Cl>[CH2:1]([N:3]([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][O:17][CH:19]1[CH2:20][CH2:21][CH2:22][CH2:23][O:18]1)[C:4]1[CH:9]=[CH:8][C:7]([Br:10])=[CH:6][CH:5]=1)[CH3:2]

Participants

6

Reactant 4

HCID 80803,4-dihydro-2H-pyranHCID 516892Sodium BicarbonateHCID 18793525N-ethyl-N-(6-hydroxyhexyl)-4-bromoanilineHCID 22338755Pyridinium p-toluenesulfonate monohydrate

Product 1

HCID 18793549N-ethyl-N-[6-(tetrahydropyran-2-yl)oxyhexyl]-4-bromoanilineYield 90%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

55.6 g (theoretical molar number: 184.1 mmols) of crude N-ethyl-N-(6-hydroxyhexyl)-4-bromoaniline was dissolved in 247 ml of chloroform. Then 24.6ml (1.5 equivalent) of 3,4-dihydro-2H-pyran and 7.0 g (0.2 equivalent) of pyridinium p-toluenesulfonate monohydrate were added. After displacement with argon, a Dimroth condenser and an argon balloon were attached to carry out reflux with heating for 5 hours. The reaction solution was cooled to room temperature, and a saturated aqueous sodium hydrogencarbonate solution was added thereto to effect neutralization, followed by extracted with chloroform. The organic layer thus formed was dried with anhydrous sodium sulfate and thereafter concentrated under reduced pressure. The residue thus obtained was purified by silica gel column chromatography (developing system: hexane/ethyl acetate=15/1) to obtain 63.3 g of N-ethyl-N-[6-(tetrahydropyran-2-yl)oxyhexyl]-4-bromoaniline (yield: 90%; a colorless oily liquid). IR Spectrum [ν(cm-1)]: 2924, 1588, 1492, 1348, 1260, 1174, 1116, 1066, 1022, 906, 864, 800; 1H-NMR Spectrum [δ(ppm)]: 1.12(t, 3H, J=7.0 Hz), 1.35-1.95(m, 14H), 3.20(t, 2H, J=7.6 Hz), 3.27-3.51(m, 4H), 3.73(m, 1H), 3.86(m, 1H), 4.57(t, 1H, J=3.6 Hz), 6.50(d, 2H, J=9.1 Hz), 7.24(d, 2H, J=9.1 Hz)

Workup

  1. temperatureto carry out reflux
  2. temperaturewith heating for 5 hours
  3. extractionby extracted with chloroform
  4. customThe organic layer thus formed
  5. dry with materialwas dried with anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue thus obtained
  8. customwas purified by silica gel column chromatography (developing system: hexane/ethyl acetate=15/1)

Sources & evidence

ORD record
ord-8aa2d72878d743faaaec940ea6d5ef9c
Source dataset
uspto-grants-2000_04
Patent number
US06051722

Reaction notes

Loading…