Water → 6-[{4-[(4-butylphenyl)ethynyl]benzyl}(hexyl)amino]-2,2-dimethyl-4H-1,3-benzodioxin-4-one

HRID 551889Notes

Reaction equation

HRID 551889 reaction equation
[CH2:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]#[C:12][C:13]2[CH:33]=[CH:32][C:16]([CH2:17][NH:18][C:19]3[CH:31]=[CH:30][C:22]4[O:23][C:24]([CH3:29])([CH3:28])[O:25][C:26](=[O:27])[C:21]=4[CH:20]=3)=[CH:15][CH:14]=2)=[CH:7][CH:6]=1)[CH2:2][CH2:3][CH3:4].[CH:34](=O)[CH2:35][CH2:36][CH2:37][CH2:38][CH3:39].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].O>ClCCCl>[CH2:1]([C:5]1[CH:6]=[CH:7][C:8]([C:11]#[C:12][C:13]2[CH:33]=[CH:32][C:16]([CH2:17][N:18]([CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39])[C:19]3[CH:31]=[CH:30][C:22]4[O:23][C:24]([CH3:29])([CH3:28])[O:25][C:26](=[O:27])[C:21]=4[CH:20]=3)=[CH:15][CH:14]=2)=[CH:9][CH:10]=1)[CH2:2][CH2:3][CH3:4]

Participants

6

Reactant 4

HCID 962WaterHCID 6184HexanalHCID 5049666Sodium triacetoxyborohydrideHCID 114761686-({4-[(4-butylphenyl)ethynyl]benzyl}amino)-2,2-dimethyl-4H-1,3-benzodioxin-4-one

Product 1

HCID 575545156-[{4-[(4-butylphenyl)ethynyl]benzyl}(hexyl)amino]-2,2-dimethyl-4H-1,3-benzodioxin-4-oneYield 92.5%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 6-({4-[(4-butylphenyl)ethynyl]benzyl}amino)-2,2-dimethyl-4H-1,3-benzodioxin-4-one (4.00 g, 9.1 mmol) in anhydrous DCE (60 mL) were added hexanal (Aldrich, 1.80 mL, 14.6 mmol) and sodium triacetoxyborohydride (6.17 g, 29.1 mmol). The resulting mixture was stirred at 70° C. overnight. Then the reaction mixture was poured into water (60 mL) and extracted with DCM (2×60 mL). The combined organic layers were dried over MgSO4 and the solvents were removed under reduced pressure to give a yellow oil. Purification by flash chromatography on silicagel (c-Hex/EtOAc (9/1)) gave 4.41 g (92%) of the title compound as a yellow oil. HPLC, Rt: 6.2 min (purity: 100%). LC/MS, M+(ESI): 524.1. 1H NMR (CDCl3) δ: 7.48 (d, J=8.3 Hz, 2H), 7.44 (d, J=8.3 Hz, 2H), 7.25 (d, J=3.0 Hz, 1H), 7.20 (d, J=8.3 Hz, 2H), 7.16 (d, J=8.3 Hz, 2H), 6.86 (dd, J=9.0, 3.0 Hz, 1H), 6.79 (d, J=9.0 Hz, 1H), 4.51 (s, 2H), 3.37 (t, J=7.7 Hz, 2H), 2.63 (t, J=7.7 Hz, 2H), 1.71 (s, 6H), 1.61 (m, 4H), 1.40-1.25 (m, 8H), 0.94 (t, J=7.3 Hz, 3H), 0.90 (t, J=6.7 Hz, 3H).

Workup

  1. extractionextracted with DCM (2×60 mL)
  2. dry with materialThe combined organic layers were dried over MgSO4
  3. customthe solvents were removed under reduced pressure
  4. customto give a yellow oil
  5. customPurification by flash chromatography on silicagel (c-Hex/EtOAc (9/1))

Sources & evidence

ORD record
ord-f84dbc23d5174627ad5368d09caf4973
Source dataset
uspto-grants-2011_05
Patent number
US07947851B2

Reaction notes

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