Triethylamine → 6-(3-chlorophenylamino)-4,4-diethyl-1-methyl-1H-benzo[d][1,3]oxazin-2(4H)-one

HRID 1296484Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1296484
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]2[N:10]([CH3:11])[C:9](=[O:12])[O:8][C:7]([CH2:15][CH3:16])([CH2:13][CH3:14])[C:6]=2[CH:17]=1.[Cl:18][C:19]1[CH:20]=[C:21](B(O)O)[CH:22]=[CH:23][CH:24]=1.C(N(CC)CC)C>C(Cl)Cl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[Cl:18][C:19]1[CH:24]=[C:23]([NH:1][C:2]2[CH:3]=[CH:4][C:5]3[N:10]([CH3:11])[C:9](=[O:12])[O:8][C:7]([CH2:15][CH3:16])([CH2:13][CH3:14])[C:6]=3[CH:17]=2)[CH:22]=[CH:21][CH:20]=1

Komponenten

6

Edukt 3

HCID 8471TriethylamineHCID 2734323(3-Chlorophenyl)boronic acidHCID 692163266-amino-4,4-diethyl-1-methyl-1,4-dihydro-2H-3,1-benzoxazin-2-one

Produkt 1

HCID 117394466-(3-chlorophenylamino)-4,4-diethyl-1-methyl-1H-benzo[d][1,3]oxazin-2(4H)-oneAusbeute 43,8 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8895Cupric acetateKatalysatorHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

To a solution of 6-amino-4,4-diethyl-1-methyl-1,4-dihydro-2H-3,1-benzoxazin-2-one (0.13 g, 0.53 mmol) and 3-chlorophenylboronic acid (0.42 g, 2.66 mmol) in methylene chloride (5 mL) was added triethylamine (0.4 mL, 2.87 mmol), and copper (II) acetate (0.19 g, 1.06 mmol) and stirred at room temperature for 2 days. The reaction was partitioned between ammonium chloride solution (sat.) and methylene chloride. The organic layer was washed with sodium bicarbonate solution (sat.), dried over magnesium sulfate, and concentrated. Flash silica gel column separation with 25% ethyl acetate/hexane followed by trituration with an ether/methylene chloride/hexane mixture gave the title compound as a white solid (0.08 g, 43%). 1H NMR (DMSO-d6): δ 8.32 (s, 1H), 7.21 (t, J=8.0 Hz, 1H), 7.13 (dd, J=8.6, 2.3 Hz, 1H), 7.05 (d, J=8.7 Hz, 1H), 6.91 (m, 2H), 6.87 (dd, J=7.6, 1.4 Hz, 1H), 6.77 (d, J=7.8 Hz, 1H), 3.27 (s, 3H), 1.97 (m, 4H), 0.82 (t, J=7.3 Hz, 6H). MS (ESI) m/z 345/347 ([M+H]+); MS (ESI) m/z 343/345 ([M−H]−); Anal. calcd for C19H21ClN2O2: C, 66.18; H, 6.14; N, 8.12. Found: C, 65.70; H, 6.01; N, 7.90.

Aufarbeitung

  1. customThe reaction was partitioned between ammonium chloride solution (sat.) and methylene chloride
  2. washThe organic layer was washed with sodium bicarbonate solution (sat.)
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. customFlash silica gel column separation with 25% ethyl acetate/hexane

Quellen und Nachweise

ORD-Eintrag
ord-288394dddd5142d98362281ca4f66ec8
Quelldatensatz
uspto-grants-2007_07
Patentnummer
US07247625B2

Notizen zur Reaktion

Wird geladen…