Acetic Acid → HCID 59807081, compound

HRID 1922446Notes

Reaction equation

HRID 1922446 reaction equation
[Br:1][C:2]1[CH:17]=[CH:16][C:5]2[N:6]([CH:11]3[CH2:15][CH2:14][NH:13][CH2:12]3)[CH2:7][CH2:8][CH2:9][CH2:10][C:4]=2[CH:3]=1.C=O.[C:20](O)(=O)C.[BH3-]C#N.[Na+].[OH-].[Na+]>CO>[Br:1][C:2]1[CH:17]=[CH:16][C:5]2[N:6]([CH:11]3[CH2:15][CH2:14][N:13]([CH3:20])[CH2:12]3)[CH2:7][CH2:8][CH2:9][CH2:10][C:4]=2[CH:3]=1

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 712FormaldehydeHCID 14798Sodium HydroxideHCID 5003444Sodium cyanoborohydrideHCID 59807055HCID 59807055, compound

Product 1

HCID 59807081HCID 59807081, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of compound 4 (0.79 g, 2.68 mmol) in anhydrous methanol (10 mL) was treated with formaldehyde (37% in H2O, 0.26 g, 3.22 mmol) followed by acetic acid (0.38 mL, 6.707 mmol) and NaCNBH3 (0.20 g, 3.22 mmol) at room temperature. The reaction mixture was stirred at room temperature for overnight (16 h). The reaction was basified with 2 N NaOH (50 mL) and the product extracted into CH2Cl2 (2×25 mL). The combined organic layers were washed with brine (25 mL), dried (Na2SO4) and concentrated. The crude product was purified by column chromatography (CH2Cl2, followed by 2 N NH3 in MeOH:CH2Cl2, 5:95) to give compound 5 (0.74 g, 90%) as a brown solid. 1H NMR (DMSO-d6) δ 1.48-1.49 (m, 2H), 1.59-1.72 (m, 3H), 2.22 (s, 3H), 2.54-2.66 (m, 5H), 2.89-2.90 (m, 2H), 3.33 (brs, 2H), 3.90-3.94 (m, 1H), 6.78 (d, 1H, J=8.5 Hz), 7.20 (dd, 1H, J=2.5, 8.5 Hz), 7.26 (d, 1H, J=2.5 Hz); ESI-MS (m/z, %): 311 (MH+, 97), 309 (100).

Workup

  1. extractionthe product extracted into CH2Cl2 (2×25 mL)
  2. washThe combined organic layers were washed with brine (25 mL)
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customThe crude product was purified by column chromatography (CH2Cl2, followed by 2 N NH3 in MeOH:CH2Cl2, 5:95)

Sources & evidence

ORD record
ord-a2d3602845134673a969662fc31d4a12
Source dataset
uspto-grants-2012_05
Patent number
US08173813B2

Reaction notes

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