Thionyl Chloride → HCID 11521640, compound

HRID 1602852Notes

Reaction equation

HRID 1602852 reaction equation
[CH2:1]1[O:12][C:11]2[CH:10]=[C:6]([C:7]([OH:9])=O)[C:5]([OH:13])=[CH:4][C:3]=2[O:2]1.S(Cl)(Cl)=O.[CH3:18][C:19]1[O:20][CH2:21][CH2:22][N:23]=1>C(Cl)(Cl)Cl>[CH3:18][C:19]12[O:20][CH2:21][CH2:22][N:23]1[C:7](=[O:9])[C:6]1[CH:10]=[C:11]3[O:12][CH2:1][O:2][C:3]3=[CH:4][C:5]=1[O:13]2

Participants

5

Reactant 3

HCID 24386Thionyl Chloride2×HCID 707132-Methyl-2-oxazolineHCID 158846296-hydroxy-1,3-dioxaindane-5-carboxylic acid

Product 1

HCID 11521640HCID 11521640, compoundYield 64%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

4,5-Methylenedioxysalicylic acid (0.472 g; 2.59 mmol) was suspended in 8 mL dry chloroform to which was added 0.476 g (4.00 mmol) thionyl chloride. The reaction mixture was heated at reflux for 3 h, during which time the suspension turned into a dark solution. The solution was allowed to cool to ambient and the solvent and excess thionyl chloride were removed in vacuo. The residue was dissolved in 8 mL methylene chloride and 0.392 g (4.60 mmol) 2-methyl-2-oxazoline was added dropwise. The solution was stirred for 1 h and then concentrated onto silica gel for subsequent purification by column chromatography (hexane/ethyl acetate=2:1) to yield 0.500 g of crude product. The product was recrystallized from ethyl acetate/hexane (1:10) to give 0.392 g (64% yield) of white crystalline solid with mp 132-133° C. IR (thin film): 1659, 1629, 1454, 1376, and 1267 cm-1. 1H NMR (500 MHz; CDCl3) δ 7.28 (1H, s), 6.48 (1H, s), 6.00 (2H, AB quartet), 4.27 (1H, dd, J=10.5 & 5.6 Hz), 4.17-4.23 (1H, m), 4.05-4.13 (1H, m), 3.55 (1H, td, J=10.6 & 6.5 Hz), and 1.59 ppm (3H, s).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 3 h, during which time the suspension
  3. customwere removed in vacuo
  4. dissolutionThe residue was dissolved in 8 mL methylene chloride
  5. concentrationconcentrated onto silica gel for subsequent purification by column chromatography (hexane/ethyl acetate=2:1)
  6. customto yield 0.500 g of crude product
  7. customThe product was recrystallized from ethyl acetate/hexane (1:10)

Sources & evidence

ORD record
ord-1bb19e03cb214f6fbcb8e68a21625066
Source dataset
uspto-grants-1999_11
Patent number
US05985871

Reaction notes

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