1,3-Propanediol → 2-(4-(tert-Butyl)-2-(1,3-dioxan-2-yl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole

HRID 1185019Notes

Reaction equation

HRID 1185019 reaction equation
[C:1]([C:5]1[CH:6]=[CH:7][C:8]([C:13]2[O:14][CH2:15][C:16]([CH3:19])([CH3:18])[N:17]=2)=[C:9]([CH:12]=1)[CH:10]=[O:11])([CH3:4])([CH3:3])[CH3:2].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.[CH2:37](O)[CH2:38][CH2:39][OH:40]>C1(C)C=CC=CC=1>[C:1]([C:5]1[CH:6]=[CH:7][C:8]([C:13]2[O:14][CH2:15][C:16]([CH3:19])([CH3:18])[N:17]=2)=[C:9]([CH:10]2[O:40][CH2:39][CH2:38][CH2:37][O:11]2)[CH:12]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 104421,3-PropanediolHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 580161935-(tert-Butyl)-2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)benzaldehyde

Product 1

HCID 594738142-(4-(tert-Butyl)-2-(1,3-dioxan-2-yl)phenyl)-4,4-dimethyl-4,5-dihydrooxazoleYield 21.7%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 101d (60 g, 0.23 mol), pyridinium p-toluenesulfonate (4 g, 0.02 mol) and 1,3-propanediol (60 mL) in toluene (500 mL) was heated to reflux overnight and cooled to room temperature upon the completion of reaction determined by LCMS. The reaction mixture was washed with 200 mL of 50 percent aqueous NaHCO3, 200 mL of water, and 200 mL of brine. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo to give a residue which was purified by silica gel chromatography using EtOAc/petroleum ether=1:5 as eluent to provide 101e (16 g, 21.7%) as a clear yellow gum. LCMS (ESI) 318 (M+H)+. 1HNMR (300 MHz, CDCl3) δ 7.79 (s, 1H), 7.67 (d, J=8.0 Hz, 1H), 7.36 (dd, J=1.6, 8.4 Hz, 1H), 6.32 (s, 1H), 4.23 (dd, J=5.2, 11.2 Hz, 2H), 4.06 (s, 2H), 4.04-3.98 (m, 2H), 2.27-2.21 (m, 1H), 1.48-1.38 (m, 1H), 1.38 (s, 6H), 1.32 (s, 9H).

Workup

  1. temperaturewas heated
  2. temperatureto reflux overnight
  3. washThe reaction mixture was washed with 200 mL of 50 percent aqueous NaHCO3, 200 mL of water, and 200 mL of brine
  4. dry with materialThe organic layer was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto give a residue which
  8. customwas purified by silica gel chromatography

Sources & evidence

ORD record
ord-5049fb6a74574447baf63b83d143ac72
Source dataset
uspto-grants-2014_03
Patent number
US08669251B2

Reaction notes

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