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

HRID 1296484Notes

Reaction equation

HRID 1296484 reaction equation
[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

Participants

6

Reactant 3

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

Product 1

HCID 117394466-(3-chlorophenylamino)-4,4-diethyl-1-methyl-1H-benzo[d][1,3]oxazin-2(4H)-oneYield 43.8%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-288394dddd5142d98362281ca4f66ec8
Source dataset
uspto-grants-2007_07
Patent number
US07247625B2

Reaction notes

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