Ethylene Glycol → HCID 19701587, compound

HRID 1844228Notes

Reaction equation

HRID 1844228 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[OH:10])[CH:5]=[O:6].[OH:11][CH2:12][CH2:13]O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[C:4]([CH:5]2[O:11][CH2:12][CH2:13][O:6]2)[CH:7]=[CH:8][C:9]=1[OH:10]

Participants

5

Reactant 3

HCID 174Ethylene GlycolHCID 6101p-Toluenesulfonic acidHCID 763083-Bromo-4-hydroxybenzaldehyde

Product 1

HCID 19701587HCID 19701587, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

3-Bromo-4-hydroxybenzaldehyde (2a, 10.0 g, 49.8 mmol) was heated at reflux with 1,2-dihydroxyethane (25 g, 0.4 mol) in toluene (150 mL) in the presence of p-toluenesulfonic acid (950 mg) for 48 h in an apparatus fitted with a Dean-Stark trap. The reaction mixture was concentrated by reduced pressure evaporation, washed with aqueous sodium hydrogen carbonate, water, brine, dried over Na2SO4, evaporated to dryness and then passed through a short silica gel column using a hexanes-ethyl acetate mixture (5:1) with a few drops of triethylamine as eluent to afford the protected product 3a (11.0 g, 95%) as a crystalline solid. Rf=0.38 (25% EtOAc-hexanes): mp 76-78° C. IR (neat) 3351, 2954, 2891, 1608, 1499, 1431, 1284, 1100 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.57 (d, J=1.8 Hz, 1H), 7.28 (dd, J=8.4, 2.4 Hz, 1H), 6.96 (d, J=8.7 Hz, 1H), 5.69 (s, 1H), 4.03 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 152.9, 131.5, 130.2, 127.5, 115.8, 110.0, 102.7, 65.2; CIMS (m/z, rel intensity) 247 (MH++2, 7), 245 (MH+, 7), 203 (100), 201 (100), 175 (4), 173(5), 94 (1).

Workup

  1. customfitted with a Dean-Stark trap
  2. concentrationThe reaction mixture was concentrated by reduced pressure evaporation
  3. washwashed with aqueous sodium hydrogen carbonate, water, brine
  4. dry with materialdried over Na2SO4
  5. customevaporated to dryness

Sources & evidence

ORD record
ord-b63c841473d441b280d7a82029c69b0c
Source dataset
uspto-grants-2015_02
Patent number
US08946287B2

Reaction notes

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