Hydrochloric Acid → HCID 69213011, compound

HRID 899223Notes

Reaction equation

HRID 899223 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[O:10])[CH3:9].[Cl:11][C:12]1[CH:17]=[CH:16][C:15]([Mg]Br)=[CH:14][CH:13]=1.C1N=CN([C:25](N2C=NC=C2)=[O:26])C=1.Cl>C1COCC1.CCOCC>[Cl:11][C:12]1[CH:17]=[CH:16][C:15]([C:8]2([CH3:9])[C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=3[NH:1][C:25](=[O:26])[O:10]2)=[CH:14][CH:13]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 110862'-AminoacetophenoneHCID 682631,1'-CarbonyldiimidazoleHCID 178478191HCID 178478191, compound

Product 1

HCID 69213011HCID 69213011, compoundYield 32%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 1-(2-aminophenyl)-ethanone (8.00 g, 59.20 mmol) in THF (200 mL) at 0° C. was slowly added 4-chlorophenyl magnesium bromide (1.0 M, 178 mL, 178 mmol) in ether. The reaction was allowed to warm to room temperature. After 3 hours, the reaction mixture was quenched with ammonium chloride solution (sat.) and extracted several times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated. The crude solid was taken up in THF (200 mL) and CDI (10.56 g, 65.10 mmol) was added. The reaction solution was stirred overnight at room temperature, poured into 1N HCl, and extracted several times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and trituration with ether gave 4-(4-chlorophenyl)-4-methyl-1,4-dihydro-2H-3,1-benzoxazin-2-one as a tan solid (5.19 g, 32%). 1H NMR (DMSO-d6): δ 10.30 (s, 1H), 7.46 (m, 3H), 7.36 (td, J=7.7, 1.0 Hz, 1H), 7.25 (d, J=8.6 Hz, 2H), 7.15 (t, J=7.6 Hz, 1H), 6.92 (d, J=7.7 Hz, 1H), 1.94 (s, 3H); MS (ESI) m/z [M+H]+=(274/276); MS (ESI) m/z [M−H]−=(272/274); Anal. calcd for C15H12ClNO2: C, 65.82; H, 4.42; N, 5.12. Found: C, 65.38; H, 4.58; N, 5.00.

Workup

  1. customat 0° C.
  2. customthe reaction mixture was quenched with ammonium chloride solution (sat.)
  3. extractionextracted several times with ethyl acetate
  4. dry with materialThe combined organic layers were dried over magnesium sulfate
  5. concentrationconcentrated
  6. extractionextracted several times with ethyl acetate
  7. dry with materialThe combined organic layers were dried over magnesium sulfate and trituration with ether

Sources & evidence

ORD record
ord-1361edee873246d19b7be5410770405b
Source dataset
uspto-grants-2008_04
Patent number
US07354915B2

Reaction notes

Loading…