Sodium Hydroxide → 2-[2-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2-oxo-ethylsulfanyl]-thiazol-4-one

HRID 916689Notes

Reaction equation

HRID 916689 reaction equation
[S:1]1[CH2:7][C:5](=[O:6])[NH:4][C:2]1=[S:3].[OH-].[Na+].Cl[CH2:11][C:12]([C:14]1[CH:23]=[CH:22][C:17]2[O:18][CH2:19][CH2:20][O:21][C:16]=2[CH:15]=1)=[O:13]>CCO.O>[O:18]1[C:17]2[CH:22]=[CH:23][C:14]([C:12](=[O:13])[CH2:11][S:3][C:2]3[S:1][CH2:7][C:5](=[O:6])[N:4]=3)=[CH:15][C:16]=2[O:21][CH2:20][CH2:19]1

Participants

6

Reactant 3

HCID 14798Sodium HydroxideHCID 1201546Rhodanine2×HCID 27801786-Chloroacetyl-1,4-benzodioxane

Product 1

HCID 589613952-[2-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2-oxo-ethylsulfanyl]-thiazol-4-one

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Rhodanine (0.052 g, 0.388 mmol, 1.0 eq.) was dissolved in EtOH (2 ml) and 2 M NaOH (0.275 ml, 0.550 mmol, 1.42 eq.) with vigorous stirring. Once the Rhodanine was completely dissolved, 6-Chloroacetyl-1,4-benzodioxane (0.080 g, 0.380 mmol, 0.98 eq.) was added with constant stirring. (It should be noted that α-chloro ketones were used when the corresponding α-bromo ketones were not available.) The reaction was mixed overnight at 40° C. After 18 hrs the reaction was removed from the heat and left stirring at room temp for 48 hrs. The resulting reaction mixture was then diluted with water (5 ml) and extracted with dichloromethane (3×5 ml). The organic layer was dried over Na2SO4 and then evaporated to yield an oil. The oil was purified by chromatotron using a 50/50 mixture of ethyl acetate in hexanes as the mobile phase. The purified product, Compound 34, was then recrystallized in hexanes to complete its purification (20 mg, 0.0646 mmol, 17%). The product was characterized by 1H-NMR: (CDCl3) 7.55 (q, 2H), 6.93 (d, 1H), 4.93 (s, 2H), 4.31 (m, 4H), 4.02 (s, 2H) ppm. In addition LCMS [ES+] analysis yielded a single peak, 310 [M]+ m/e.

Workup

  1. addition) The reaction was mixed overnight at 40° C
  2. customAfter 18 hrs the reaction was removed from the
  3. temperatureheat
  4. waitleft
  5. customThe resulting reaction mixture
  6. extractionextracted with dichloromethane (3×5 ml)
  7. dry with materialThe organic layer was dried over Na2SO4
  8. customevaporated
  9. customto yield an oil
  10. customThe oil was purified by chromatotron
  11. additiona 50/50 mixture of ethyl acetate in hexanes as the mobile phase
  12. customThe purified product, Compound 34, was then recrystallized in hexanes
  13. customits purification (20 mg, 0.0646 mmol, 17%)
  14. additionIn addition LCMS [ES+] analysis
  15. customyielded a single peak, 310 [M]+ m/e

Sources & evidence

ORD record
ord-411c3bbeda2f467eb491a9bf461b568a
Source dataset
uspto-grants-2007_09
Patent number
US07271195B2

Reaction notes

Loading…