Acetonitrile → acrylic acid 4-{3-[2-(1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetoxy]-2-hydroxy-propoxy}-butyl ester

HRID 876067Notes

Reaction equation

HRID 876067 reaction equation
[F:1][C:2]1[C:15]2[C:14](=[O:16])[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[S:7][C:6]=2[C:5]([O:17][CH2:18][C:19]([OH:21])=[O:20])=[CH:4][CH:3]=1.C(#N)C.[OH:25][CH2:26][CH2:27][CH2:28][CH2:29][O:30][C:31](=[O:34])[CH:32]=[CH2:33].[CH2:35](OCC1OC1)[CH:36]1[O:38][CH2:37]1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C.CC(N(C)C)=O>[F:1][C:2]1[C:15]2[C:14](=[O:16])[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[S:7][C:6]=2[C:5]([O:17][CH2:18][C:19]([O:21][CH2:35][CH:36]([OH:38])[CH2:37][O:25][CH2:26][CH2:27][CH2:28][CH2:29][O:30][C:31](=[O:34])[CH:32]=[CH2:33])=[O:20])=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 6342AcetonitrileHCID 223231504-Hydroxybutylacrylate glycidyletherHCID 67286258(1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid

Product 1

HCID 67472861acrylic acid 4-{3-[2-(1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetoxy]-2-hydroxy-propoxy}-butyl esterYield 114.3%

Reagents, catalysts & solvents 3

HCID 314042,6-Di-tert-butyl-4-methylphenolCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
94 °C

Procedure

A reaction mixture containing (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid (4.0 g, 13 mmol), acetonitrile (65 mL), dimethylacetamide (30 ml), tetrabutylammonium bromide (0.4 g, 1.3 mol), 2,6-di-tert-butyl-4-methylphenol (0.03 g, 0.00013 mol) and 4-hydroxybutylacrylate glycidylether (2.6 g, 13 mmol) was heated to reflux (94° C.). The mixture was allowed to stir at reflux temperature for 24 hours. The solvent was removed under reduced pressure. The residual oil was dissolved in dichloromethane (100 mL) and extracted with a mixture of distilled water (50 ml) and an aqueous solution of sodium hydroxide 1N (50 mL). The organic layer was isolated and dried over MgSO4. Evaporation of the solvent under reduced pressure yielded 7.5 g of the crude acrylic acid 4-{3-[2-(1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetoxy]-2-hydroxy-propoxy}-butyl ester. The product was purified on a Merck Super Vario Prep Column using dichloromethane/ethyl acetate (75/25) as eluent, yielding 2.8 g of 4-{3-[2-(1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetoxy]-2-hydroxy-propoxy}-butyl ester as a yellow oil.

Workup

  1. temperaturewas heated
  2. temperatureat reflux temperature for 24 hours
  3. customThe solvent was removed under reduced pressure
  4. dissolutionThe residual oil was dissolved in dichloromethane (100 mL)
  5. extractionextracted with a mixture of distilled water (50 ml)
  6. customThe organic layer was isolated
  7. dry with materialdried over MgSO4
  8. customEvaporation of the solvent under reduced pressure

Sources & evidence

ORD record
ord-276acbdbf562442593296ff3b73c06fd
Source dataset
uspto-grants-2015_03
Patent number
US08985753B2

Reaction notes

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