Ammonium Acetate → HCID 19379391, compound

HRID 2210698Notes

Reaction equation

HRID 2210698 reaction equation
C([O-])(=[O:3])C.[NH4+].C[O-].[Na+].[N+]([CH:12]1[CH:17]([C:18]2[S:19][CH:20]=[CH:21][CH:22]=2)[NH:16][C:15](=[O:23])[CH2:14][CH2:13]1)([O-])=O>Cl.CO.[Cl-].[Cl-].[Cl-].[Ti+3]>[O:23]=[C:15]1[CH2:14][CH2:13][C:12](=[O:3])[CH:17]([C:18]2[S:19][CH:20]=[CH:21][CH:22]=2)[NH:16]1

Participants

7

Reactant 3

HCID 517165Ammonium AcetateHCID 601531HCID 601531, compoundHCID 10942334Sodium Methoxide

Product 1

HCID 19379391HCID 19379391, compound

Reagents, catalysts & solvents 3

HCID 10313229titanium(III) trichlorideCatalyst2×HCID 313Hydrochloric AcidSolventHCID 887MethanolSolvent3×

Procedure

A 13% solution of titanium trichloride in 20% hydrochloric acid (173 ml) was added to a degassed solution of ammonium acetate (100 g) in methanol (300 ml) at 0° C. under nitrogen over 20 min. A solution of sodium methoxide (1.49 g) in methanol (60 ml) was added to a suspension of 5-nitro-2-oxo-6-thienylpiperidine (5 g, Example 25a) in methanol (75 ml) and the mixture stirred for 20 min. This solution was then added dropwise to the titanium trichloride/buffer solution at 0° C. under nitrogen. The reaction was stirred at 0° C. for 30 min and at 23° C. for 30 min. Methanol was removed in vacuo and ethyl acetate was added to the residue. The emulsion was filtered through Hi-flo and then shaken with brine. The organic phase was dried (MgSO4) and concentrated in vacuo. The material was chromatographed on silica using (1:1 then 9:1) ethyl acetate in petroleum ether (60-80) as eluant to give 2,5-dioxo-6-thienylpiperidine. m/z (CI+) m/z 105 (MH, 53%).

Workup

  1. stirringThe reaction was stirred at 0° C. for 30 min and at 23° C. for 30 min
  2. customMethanol was removed in vacuo and ethyl acetate
  3. additionwas added to the residue
  4. filtrationThe emulsion was filtered through Hi-flo
  5. stirringshaken with brine
  6. dry with materialThe organic phase was dried (MgSO4)
  7. concentrationconcentrated in vacuo
  8. customThe material was chromatographed on silica using (1:1

Sources & evidence

ORD record
ord-5e9c51bb2ad3432daaa558d05f5403c2
Source dataset
uspto-grants-1995_10
Patent number
US05459270

Reaction notes

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