Vanillin → 3-Methoxy-4-prop-2-ynyloxy-benzaldehyde

HRID 2175677Notes

Reaction equation

HRID 2175677 reaction equation
[CH2:1](Br)[C:2]#[CH:3].[O:5]=[CH:6][C:7]1[CH:15]=[CH:14][C:12]([OH:13])=[C:9]([O:10][CH3:11])[CH:8]=1.C(=O)([O-])[O-].[K+].[K+]>CC#N>[CH3:11][O:10][C:9]1[CH:8]=[C:7]([CH:15]=[CH:14][C:12]=1[O:13][CH2:3][C:2]#[CH:1])[CH:6]=[O:5]

Participants

5

Reactant 3

HCID 1183VanillinHCID 7842Propargyl bromideHCID 11430Potassium Carbonate

Product 1

HCID 31440663-Methoxy-4-prop-2-ynyloxy-benzaldehydeYield 97%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Propargyl bromide (293 mL, 80% w/v, 1.97 mol) was added to a suspension of vanillin (250 g, 1.64 mol) and potassium carbonate (681 g, 4.93 mol) in MeCN (2.0 L). The suspension was heated to reflux for 6 h and the solvent was removed under reduced pressure. Water was added and the aqueous phase was extracted with EtOAc, washed with water, brine and dried. The solvent was removed under reduced pressure to give 3-methoxy-4-propargyloxybenzaldehyde (302 g, 97%) as yellow crystalline solid; mp 95° C.; δH (400 MHz, CDCl3) 2.56 (t, J=2.5 Hz, 1H, C≡CH), 3.95 (s, 3H, OCH3), 4.86 (d, J=2.5 Hz, 2H, OCH2); 7.14 (d, J5,6=6.8 Hz, 1H, H5), 7.44 (d, J2,6=1.4 Hz, 1H, H2), 7.47 (dd, J5,6=6.8, J2,6=1.4 Hz, 1H, H6), 9.87 (s, 1H, CHO); δC (100 MHz, CDCl3) 56.0, 56.6, 77.2, 77.4, 109.4, 112.5, 126.3, 130.9, 150.0, 152.1, 190.9; HRMS (ESI) Calculated for C11H10O3 [M+H]+, 191.0703 found 191.0706; νmax 1006, 1130, 1259, 1586, 1677, 2119, 2845, 2932, 3266 cm−1.

Workup

  1. temperatureThe suspension was heated
  2. temperatureto reflux for 6 h
  3. customthe solvent was removed under reduced pressure
  4. additionWater was added
  5. extractionthe aqueous phase was extracted with EtOAc
  6. washwashed with water, brine
  7. customdried
  8. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-b20e06ee9def43b1a32688d0015a3104
Source dataset
uspto-grants-2015_06
Patent number
US09062076B2

Reaction notes

Loading…