Ethyl bromoacetate → (9-Cyano-9H-thioxanthen-9-yl)-acetic acid ethyl ester

HRID 393261Notes

Reaction equation

HRID 393261 reaction equation
[CH:1]1[C:14]2[CH:13]([C:15]#[N:16])[C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[S:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.C([Li])CCC.[CH3:22][CH2:23][O:24][C:25]([CH2:27]Br)=[O:26]>CCOCC>[CH2:23]([O:24][C:25](=[O:26])[CH2:27][C:13]1([C:15]#[N:16])[C:14]2[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=2[S:6][C:7]2[C:12]1=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH3:22]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 123928179H-Thioxanthene-9-carbonitrileHCID 178418339Butyllithium

Product 1

HCID 12132646(9-Cyano-9H-thioxanthen-9-yl)-acetic acid ethyl esterYield 59%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

9H-thioxanthene-9-carbonitrile [33] (1.20 g, 5.37 mmol) was dissolved in anhydrous Et2O and cooled in an icebath. n-Butyl lithium (2.14 mL, 5.37 mmol, 2.5M soln. in hexanes) was added dropwise over 10 min. with continuous stirring. Stirring was continued for 30 min. at the same temperature and then brought to room temperature. The reaction mixture was heated at reflux (1 hr), cooled in an icebath and ethyl bromo acetate (0.83 mL, 7.52 mmol) was added dropwise via syringe. The resulting mixture was heated at reflux (4 h) cooled and filtered. The residue was washed with ether (25 mL). Water (25 mL) was added to the filterate and the organic layer was separated. The aqueous layer was once again extracted with ether (25 mL). The combined ether extracts were washed with water and brine, dried (MgSO4) and evaporated under reduced pressure to give an oil which was purified by mplc using pet. ether: EtOAc (9:1) as eluent to give 0.97 g (59%) of the product as a colorless oil. 1H NMR (CDCl3)d: 1.08-1.12 (t, J=6 Hz, CH3), 3.08 (s, 2H, CH2), 3.95-4.03 (q, 2H, CH2), 7.31-8.00 (m, 8H, Ar—H). 13C NMR (CDCl3)d: 38.49, 47.63, 60.76, 118.91, 127.00, 127.24, 127.80, 128.15, 130.73, 130.98, 167.66.

Workup

  1. temperaturecooled in an icebath
  2. custombrought to room temperature
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux (1 hr)
  5. additionwas added dropwise via syringe
  6. temperatureThe resulting mixture was heated
  7. temperatureat reflux (4 h)
  8. temperaturecooled
  9. filtrationfiltered
  10. washThe residue was washed with ether (25 mL)
  11. additionWater (25 mL) was added to the filterate
  12. customthe organic layer was separated
  13. extractionThe aqueous layer was once again extracted with ether (25 mL)
  14. washThe combined ether extracts were washed with water and brine
  15. dry with materialdried (MgSO4)
  16. customevaporated under reduced pressure
  17. customto give an oil which
  18. customwas purified by mplc

Sources & evidence

ORD record
ord-2514f33ad25d44a2803578b604524f2b
Source dataset
uspto-grants-2004_10
Patent number
US06806283B2

Reaction notes

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