Acetic Acid → HCID 44440689, compound

HRID 545487Notes

Reaction equation

HRID 545487 reaction equation
C(O[C:4]([C:6]1[S:10][C:9]2[CH:11]=[C:12]([CH:15]=O)[CH:13]=[CH:14][C:8]=2[CH:7]=1)=[O:5])C.[CH2:17]([NH2:24])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C.C([O-])(O)=O.[Na+].Cl.[NH2:49][OH:50].C[O-].[Na+]>ClC(Cl)C>[OH:50][NH:49][C:4]([C:6]1[S:10][C:9]2[CH:11]=[C:12]([CH2:15][NH:24][CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH:13]=[CH:14][C:8]=2[CH:7]=1)=[O:5]

Participants

9

Reactant 7

HCID 176Acetic AcidHCID 7504BenzylamineHCID 443297Hydroxyamine hydrochlorideHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 10942334Sodium MethoxideHCID 57443969Ethyl 6-formylbenzo[b]thiophene-2-carboxylate

Product 1

HCID 44440689HCID 44440689, compound

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

To a solution of 6-formyl-benzo[b]thiophene-2-carboxylic acid ethyl ester (85 mg, 0.36 mmol) and benzylamine (51 μL, 0.47 mmol) in anhydrous dichloroethane (5 mL) were added sodium triacetoxyborohydride (230 mg, 1.08 mmol) and acetic acid (20 μL, 0.35 mmol). After the reaction was complete, 5 mL of saturated NaHCO3 was added. The organic layer was separated, washed with 5 mL of water and then concentrated. After drying under high vacuum, the residue was dissolved in anhydrous MeOH (5 mL) and hydroxylamine hydrochloride (95 mg, 1.37 mmol) was added, followed by the addition of NaOMe solution (4.37 M in MeOH, 0.60 mL, 2.6 mmol). The mixture was allowed to stir at rt till the reaction was complete. The reaction mixture was concentrated and the residue was dissolved in a minimal amount of water. The obtained solution was acidified with 2N HCl to pH≈8. The solid formed was filtered, washed with water, collected and purified by flash column chromatography to give 6-(benzylamino-methyl)-benzo[b]thiophene-2-carboxylic acid hydroxyamide as a pale solid. 1H NMR (DMSO-d6, 200 MHz) δ 7.94 (d, J=8.4 Hz, 1H), 7.88 (s, 1H), 7.85 (s, 1H), 7.44 (dd, J=8.4, 1.4 Hz, 1H), 7.21 (t, J=7.6 Hz, 1H), 7.00-6.72 (m, 3H), 3.78 (s, 2H), 3.73 (s, 3H), 3.66 (s, 2H). MS (EI): cal'd 343.1 (MH+), exp 343.2 (MH+). 1H NMR (DMSO-d6, 200 MHz) δ 7.94 (s, 1H), 7.90-7.78 (m, 2H), 7.46-7.14 (m, 6H), 3.80 (s, 2H), 3.69 (s, 2H). MS (EI): cal'd 313.1 (MH+), exp 313.1 (MH+).

Workup

  1. customThe organic layer was separated
  2. washwashed with 5 mL of water
  3. concentrationconcentrated
  4. customAfter drying under high vacuum
  5. dissolutionthe residue was dissolved in anhydrous MeOH (5 mL)
  6. concentrationThe reaction mixture was concentrated
  7. dissolutionthe residue was dissolved in a minimal amount of water
  8. customThe solid formed
  9. filtrationwas filtered
  10. washwashed with water
  11. customcollected
  12. custompurified by flash column chromatography

Sources & evidence

ORD record
ord-6b688221b7654987b1f09cf73cc34598
Source dataset
uspto-grants-2011_05
Patent number
US07935724B2

Reaction notes

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