Hexanal → HCID 57554568, compound

HRID 551948Notes

Reaction equation

HRID 551948 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]#[C:10][C:11]2[CH:31]=[CH:30][C:14]([CH2:15][NH:16][C:17]3[CH:29]=[CH:28][C:20]4[O:21][C:22]([CH3:27])([CH3:26])[O:23][C:24](=[O:25])[C:19]=4[CH:18]=3)=[CH:13][CH:12]=2)=[CH:5][CH:4]=1.[CH:32](=O)[CH2:33][CH2:34][CH2:35][CH2:36][CH3:37].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C([O-])(O)=O.[Na+]>ClCCCl.C(O)(=O)C>[CH2:32]([N:16]([CH2:15][C:14]1[CH:30]=[CH:31][C:11]([C:10]#[C:9][C:6]2[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=2)=[CH:12][CH:13]=1)[C:17]1[CH:29]=[CH:28][C:20]2[O:21][C:22]([CH3:27])([CH3:26])[O:23][C:24](=[O:25])[C:19]=2[CH:18]=1)[CH2:33][CH2:34][CH2:35][CH2:36][CH3:37]

Participants

7

Reactant 4

HCID 6184HexanalHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 575545066-({4-[(4-methoxyphenyl)ethynyl]benzyl}amino)-2,2-dimethyl-4H-1,3-benzodioxin-4-one

Product 1

HCID 57554568HCID 57554568, compoundYield 103.5%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 176Acetic AcidSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 6-({4-[(4-methoxyphenyl)ethynyl]benzyl}amino)-2,2-dimethyl-4H-1,3-benzodioxin-4-one (416 mg; 1.01 mmol) in anhydrous DCE (15 mL) were added hexanal (Aldrich, 181 μl; 1.51 mmol), sodium triacetoxyborohydride (426 mg, 2.01 mmol) and acetic acid (115 μl). The resulting mixture was heated at 70° C. under nitrogen atmosphere for 24 h and poured into a saturated aqueous solution of NaHCO3. The aqueous layer was extracted with DCM (twice) and combined organic layers were washed with brine, dried over magnesium sulfate, filtrated and concentrated. Purification by flash chromatography on silica gel (EtOAc/c-Hex 5:95 then 10:90) gave 520 mg of the title compound (quantitative). HPLC, Rt : 5.82 min (purity: 99.9%). LC/MS, M+(ESI): 498.7. 1H NMR (CDCl3) δ: 7.43 (d, J=8.9 Hz, 4H), 7.21 (s, 1H), 7.16 (d, J=8.1 Hz, 2H), 6.74-6.86 (m, 4H), 4.48 (s, 2H), 3.80 (s, 3H), 3.34 (t, J=7.8 Hz, 2H), 1.68 (s, 6H), 1.61 (m, 2H), 1.27 (s, 6H), 0.86 (m, 3H).

Workup

  1. extractionThe aqueous layer was extracted with DCM (twice) and
  2. washwere washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltrated
  5. concentrationconcentrated
  6. customPurification by flash chromatography on silica gel (EtOAc/c-Hex 5:95

Sources & evidence

ORD record
ord-02a2f5af85eb41559a75033cd2296814
Source dataset
uspto-grants-2011_05
Patent number
US07947851B2

Reaction notes

Loading…