Veratrylamine → HCID 44633762, compound

HRID 1802357Notes

Reaction equation

HRID 1802357 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[O:11][CH3:12])[CH2:6][NH2:7].C[Al](C)C.[F:17][C:18]1[C:23]([C:24]2[CH:25]=[C:26]([C:36](OC)=[O:37])[C:27]([C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=3)=[N:28][CH:29]=2)=[CH:22][C:21]([CH3:40])=[CH:20][N:19]=1>C1(C)C=CC=CC=1.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[O:11][CH3:12])[CH2:6][NH:7][C:36]([C:26]1[C:27]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=2)=[N:28][CH:29]=[C:24]([C:23]2[C:18]([F:17])=[N:19][CH:20]=[C:21]([CH3:40])[CH:22]=2)[CH:25]=1)=[O:37]

Participants

6

Reactant 3

HCID 79832VeratrylamineHCID 16682925TrimethylaluminumHCID 59187371HCID 59187371, compound

Product 1

HCID 44633762HCID 44633762, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 3,4-dimethoxybenzylamine (0.15 g, 0.89 mmol, 8.0 equiv) in toluene (2.2 mL) was added a solution of trimethylaluminum (0.39 mL, 0.78 mmol, 7.0 equiv, 2 M in toluene) at ambient temperature and the reaction mixture was stirred for 45 minutes. To the reaction mixture was added a solution of methyl 2″-fluoro-5″-methyl-2,2′:5′,3″-terpyridine-3′-carboxylate (0.036 g, 0.11 mmol, 1.0 equiv) in toluene (2 mL) and the reaction mixture was heated to 100° C. for 15 h. The reaction mixture was cooled and diluted with ethyl acetate (30 mL) and quenched with Rochelle's salts (20 mL, saturated solution). The organic phase was washed with Rochelle's salts (3×20 mL, saturated solution), dried over magnesium sulfate and concentrated. The residue was purified via normal phase chromatography (15 to 100% EtOAc in hexanes, silica) to afford the desired product (11-4) as a white solid after concentration. 1H NMR (500 MHz, CDCl3) δ 8.92-8.90 (m, 1H), 8.35 (d, J=4.0 Hz, 1H), 8.25 (bs, 1H), 8.07 (bs, 1H), 8.02 (d, J=7.6 Hz, 1H), 7.82 (td, J=7.6, 1.6 Hz, 1H), 7.78 (dd, J=9.6, 2.0 Hz, 1H), 7.70 (bs, 1H), 7.30-7.27 (m, 1H), 6.83-6.79 (m, 3H), 4.51 (d, J=5.6 Hz, 2H), 3.88 (s, 3H), 3.81 (s, 3H), 2.41 (s, 3H). HRMS [M+H] C26H23FN4O3 calc'd 459.1827. found 459.1827.

Workup

  1. temperatureThe reaction mixture was cooled
  2. customquenched with Rochelle's salts (20 mL, saturated solution)
  3. washThe organic phase was washed with Rochelle's salts (3×20 mL, saturated solution)
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified via normal phase chromatography (15 to 100% EtOAc in hexanes, silica)

Sources & evidence

ORD record
ord-f329c4db01da4d73930cd4c3ce50bcb7
Source dataset
uspto-grants-2013_01
Patent number
US08349872B2

Reaction notes

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