Acetic Acid → HCID 18947947, compound

HRID 1768501Notes

Reaction equation

HRID 1768501 reaction equation
[Cl:1][C:2]1[CH:23]=[CH:22][C:5]2[N:6]=[C:7]([O:9][C:10]3[CH:15]=[CH:14][C:13]([C:16]([CH3:21])([OH:20])[C:17]([O-:19])=O)=[CH:12][CH:11]=3)[S:8][C:4]=2[CH:3]=1.[C:24](N1C=CN=C1)(N1C=CN=C1)=[O:25].[C:36]1([NH:42][NH2:43])[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.C(O)(=O)C.[N-]1C=CN=C1>C(Cl)Cl>[Cl:1][C:2]1[CH:23]=[CH:22][C:5]2[N:6]=[C:7]([O:9][C:10]3[CH:15]=[CH:14][C:13]([C:16]4([CH3:21])[O:20][C:24](=[O:25])[N:43]([NH:42][C:36]5[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=5)[C:17]4=[O:19])=[CH:12][CH:11]=3)[S:8][C:4]=2[CH:3]=1

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 7516PhenylhydrazineHCID 682631,1'-CarbonyldiimidazoleHCID 3386966ImidazolateHCID 18947948HCID 18947948, compound

Product 1

HCID 18947947HCID 18947947, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To a solution of 2-(4-(6-chloro-2-benzothiazolyloxy)phenyl)lactate (1.56 g, 4.1 mmol(in CH2Cl2 (20 mL) was added 1,1'-carbonyldiimidazole (0.86 g, 5.3 mmol) and the resulting mixture was heated at reflux overnight. The solution was diluted with CH2Cl2 (20 mL) and then washed with H2O (two-times with 20 mL) and brine (20 mL). The organic phase was dried (MgSO4) and concentrated under vacuum. The residue was dissolved in CH2Cl2 (20 mL) and PhNHNH2 (0.77 g, 7.8 mmol) and acetic acid (0.45 mL, 7.8 mmol) were added and the resulting mixture was stirred at room temperature until thin layer chromatography indicated no imidazolide remained, approximately 36 h. The mixture was diluted with CH2Cl2 (20 mL) and washed with 1N aqueous HCl (10 mL) and H2O (10 mL). The organic phase was dried (MgSO4) and concentrated under vacuum to yield a red solid, 1.92 g, which was subjected to purification by column chromatography (140 g SiO2 eluting with 3:2:5 diethyl ether/CH2Cl2 /hexanes increasing to a ratio of 4:3:3 diethyl ether/CH2Cl2 /hexanes thereby affording the product of Step B as a light yellow powder, 0.37 g; (19%); m.p. 207°-209° C.; IR (mineral oil): 1820, 1755, 1594, 1245 cm-1 ; 1H NMR (CDCl3); δ7.7 (m,3H), 7.65 (d,1H), 7.5 (d,2H), 7.4 (d,1H), 7.3 (m,2H), 7.0 (t,1H), 6.8 (d,2H), 6.1 (s,1H), 2.0 (s,3H).

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureat reflux overnight
  3. washwashed with H2O (two-times with 20 mL) and brine (20 mL)
  4. dry with materialThe organic phase was dried (MgSO4)
  5. concentrationconcentrated under vacuum
  6. dissolutionThe residue was dissolved in CH2Cl2 (20 mL)
  7. washwashed with 1N aqueous HCl (10 mL) and H2O (10 mL)
  8. dry with materialThe organic phase was dried (MgSO4)
  9. concentrationconcentrated under vacuum
  10. customto yield a red solid, 1.92 g, which
  11. customwas subjected to purification by column chromatography (140 g SiO2 eluting with 3:2:5 diethyl ether/CH2Cl2 /hexanes increasing to a ratio of 4:3:3 diethyl ether/CH2Cl2 /hexanes

Sources & evidence

ORD record
ord-a5ba57a77e2048d482110a583a1f0422
Source dataset
uspto-grants-1995_01
Patent number
USH0001401

Reaction notes

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