Hydrogen Bromide → HCID 88627039, compound

HRID 1194914Notes

Reaction equation

HRID 1194914 reaction equation
[S:1]1[CH2:5][CH2:4][CH:3]([O:6]/[N:7]=[C:8](/[C:14](=[O:16])[CH3:15])\[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH2:2]1.[BrH:17].BrBr>C(Cl)(Cl)(Cl)Cl.ClCCl.CO.C(O)(=O)C>[Br:17][CH2:15][C:14](=[O:16])/[C:8](=[N:7]/[O:6][CH:3]1[CH2:4][CH2:5][S:1][CH2:2]1)/[C:9]([O:11][CH2:12][CH3:13])=[O:10]

Participants

8

Reactant 3

HCID 260Hydrogen BromideHCID 24408BromineHCID 140352840HCID 140352840, compound

Product 1

HCID 88627039HCID 88627039, compoundYield 23%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolvent

Procedure

Ethyl (Z)-2-(tetrahydrothien-3-yloxyimino)-3-oxo-butyrate (1.29 g) was dissolved in a mixture of carbontetrachloride (15 ml), dichloromethane (5 ml) and methanol (2 ml). The mixture was cooled to -26°, a solution of hydrogen bromide in acetic acid (0.05 ml, 45% w/v) was added followed by bromine (0.29 ml). The mixture was allowed to warm to room temperature and stirred for 3 dyys. The solvents were removed under reduced pressure, the residue was partitioned between ethyl acetate and water. The organic layer was washed successively with saturated aqueous sodium bicarbonate, water and brine, then dried (MgSO4) and evaporated. Purification by flash chromatography with dichloromethane elution gave the title compound (0.4 g, 23%) as a pale yellow liquid. νmax (film) 2970, 2940, 1740, 1695, and 1600 cm-1. δH (CDCl3) 1.34 (3H, t), 2.04 (1H, m), 2.48 (1H, m), 2.90 (2H, m), 3.13 (2H, m), 4.33 (2H, s), 4.37 (2H, q), and 5.18 (1H, m). [Mass spectrum: +ve ion MH+ (324)].

Workup

  1. temperatureThe mixture was cooled to -26°
  2. customThe solvents were removed under reduced pressure
  3. customthe residue was partitioned between ethyl acetate and water
  4. washThe organic layer was washed successively with saturated aqueous sodium bicarbonate, water and brine
  5. dry with materialdried (MgSO4)
  6. customevaporated
  7. customPurification by flash chromatography
  8. washwith dichloromethane elution

Sources & evidence

ORD record
ord-55ed3f60085f4200849bff1612831fc2
Source dataset
uspto-grants-1989_03
Patent number
US04816452

Reaction notes

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