Acetic Acid → 6-[(hexylamino)methyl]-2,2-dimethyl-4H-1,3-benzodioxin-4-one

HRID 551923Notes

Reaction equation

HRID 551923 reaction equation
[CH3:1][C:2]1([CH3:15])[O:7][C:6]2[CH:8]=[CH:9][C:10]([CH:12]=O)=[CH:11][C:5]=2[C:4](=[O:14])[O:3]1.[CH2:16]([NH2:22])[CH2:17][CH2:18][CH2:19][CH2:20][CH3:21].C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl.C(Cl)Cl>[CH2:16]([NH:22][CH2:12][C:10]1[CH:9]=[CH:8][C:6]2[O:7][C:2]([CH3:15])([CH3:1])[O:3][C:4](=[O:14])[C:5]=2[CH:11]=1)[CH2:17][CH2:18][CH2:19][CH2:20][CH3:21]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 8102HexylamineHCID 5049666Sodium triacetoxyborohydrideHCID 575545102,2-Dimethyl-4-oxo-4H-benzo[d][1,3]dioxine-6-carbaldehyde

Product 1

HCID 575545526-[(hexylamino)methyl]-2,2-dimethyl-4H-1,3-benzodioxin-4-oneYield 87.1%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 2,2-dimethyl-4-oxo-4H-1,3-benzodioxine-6-carbaldehyde (510 mg, 2.47 mmol) in anhydrous DCE (20 mL) was added n-hexylamine (392 μL, 2.97 mmol), acetic acid (212 μL) and sodium triacetoxyborohydride (786 mg, 3.71 mmol) and the resulting mixture was stirred at rt for 3 hrs. The reaction mixture was diluted with DCM and washed with a saturated aqueous solution of NaHCO3 and brine. The organic layer was dried over MgSO4 and the solvents were removed under reduced pressure. Purification by flash chromatography on silicagel (EtOAc/c-Hex (20/80)) gave 627 mg (87%) of the title compound. HPLC, Rt: 2.70 min purity: 86.4% ). 1H NMR (CDCl3) δ: 0.85 (t, J=6.8 Hz, 3H), 1.28 (m, 6H), 1.48 (m, 2H), 1.70 (s, 6H), 2.41 (m, 1H), 2.58 (t, J=7.3 Hz, 2H), 3.74 (s, 2H), 6.90 (d, J=8.5 Hz, 1H), 7.53 (dd, J=8.5, 2.3 Hz, 1H), 7.86 (d, J=2.1 Hz, 1H).

Workup

  1. washwashed with a saturated aqueous solution of NaHCO3 and brine
  2. dry with materialThe organic layer was dried over MgSO4
  3. customthe solvents were removed under reduced pressure
  4. customPurification by flash chromatography on silicagel (EtOAc/c-Hex (20/80))

Sources & evidence

ORD record
ord-51f314645c85462bb1c1d0d039941920
Source dataset
uspto-grants-2011_05
Patent number
US07947851B2

Reaction notes

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