Ethanol → HCID 12424623, compound

HRID 126986Notes

Reaction equation

HRID 126986 reaction equation
C([O-])(=O)C.[K+].C(O)C.[NH2:9][NH:10][C:11]([NH2:13])=[S:12].Cl[CH2:15][C:16](=O)[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19]>O>[NH:10]([C:11]1[S:12][CH:15]=[C:16]([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])[N:13]=1)[NH2:9]

Participants

6

Reactant 4

HCID 702EthanolHCID 69484Ethyl 4-chloroacetoacetateHCID 517044Potassium AcetateHCID 2723789Thiosemicarbazide

Product 1

HCID 12424623HCID 12424623, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Potassium acetate (1.3 g., 12.5 mmoles) was dissolved in 40 ml. of an aqueous ethanol mixture (1:1). With stirring, thiosemicarbazide (1.1 g., 12.5 mmoles) and ethyl 4-chloroacetoacetate (2.0 g., 12.5 mmoles) were introduced. After 3 hours of stirring at room temperature a red oil settled out. The reaction mixture was diluted with water and extracted several times with methylene chloride (total 100 ml.). Combined extracts were dried (calcium chloride), filtered, and concentrated under reduced pressure to approximately 2.0 g. of oily residue. Thin layer chromatography (chloroform) revealed the presence of two compounds. This oil was then chromatographed on a silica gel column using methylene chloride as the eluent. Compound IVA (see Example 12) was in the first few fractions while the latter fractions contained a single component (0.6 g.) characterized as Compound IIA by pmr. Although Compound IIA was chromatographically pure, it would not crystallize; ir (mull): 3450-3200 (N--H), 1725 (C=O), 1620, 1580 (C=N) cm-1 : pmr (deuteriochloroform): δ1.20 (t, 3H, CH3), 3.55 (s, 2H, CH2CO), 4.15 (q, 2H, OCH2), 5.80-6.20 (s-broad, 3H, NH), 6.30 (s, 1H, vinyl); ms: (m/e)201(M+).

Workup

  1. stirringAfter 3 hours of stirring at room temperature a red oil
  2. extractionextracted several times with methylene chloride (total 100 ml.)
  3. dry with materialCombined extracts were dried (calcium chloride)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure to approximately 2.0 g
  6. customThis oil was then chromatographed on a silica gel column
  7. customit would not crystallize

Sources & evidence

ORD record
ord-eb7c453ea8af4e3c9a0d49c20a5f8ac6
Source dataset
uspto-grants-1981_03
Patent number
US04254259

Reaction notes

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