2H-1,4-benzoxazin-3(4H)-one → HCID 19077119, compound

HRID 964500Notes

Reaction equation

HRID 964500 reaction equation
[O:1]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[NH:4][C:3](=O)[CH2:2]1.Cl[C:13]([CH3:21])([CH2:15][CH2:16][C:17](Cl)([CH3:19])[CH3:18])[CH3:14].[Cl-].[Al+3].[Cl-].[Cl-].C(C(C(C([O-])=O)O)O)([O-])=O.[K+].[Na+]>ClCCl.C1COCC1>[CH3:18][C:17]1([CH3:19])[CH:16]=[CH:15][C:13]([CH3:21])([CH3:14])[C:8]2[C:9]1=[CH:10][C:5]1[NH:4][CH2:3][CH2:2][O:1][C:6]=1[CH:7]=2

Participants

7

Reactant 4

HCID 727572H-1,4-benzoxazin-3(4H)-oneHCID 80360Hexane, 2,5-dichloro-2,5-dimethyl-HCID 6451240Aluminum(III) ChlorideHCID 9855836Potassium sodium tartarate

Product 1

HCID 19077119HCID 19077119, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 6-6-9-9-tetramethyl-6,9-dihydro-4H-naphtho[2,3-b][1,4]oxazin-3-one (400 mg, 1.5 mmol) [prepared by Friedel Crafts alkylation/annulation of 2H-1,4-benzoxazin-3-(4H)-one with 2,5-dichloro-2,5-dimethyl hexane in the presence of aluminum chloride at ambient temperatue (24° C.) in dichloromethane]in THF at ambient temperature was added LiA1H4 (4.6 ml, 4.6 mmol). The reaction mixture was allowed to stir and then was heated to 80° C. for 30 min. The reaction mixture was poured over saturated sodium potassium tartrate solution (100 ml), extracted with EtOAc (100 ml), dried with anhydrous MgSO4 (0.5 g), and concentrated to give 6,6,9,9-tetramethyl-3,4,6,9-tetrahydro-2H-naphtho[2,3-b][1,4]oxazine (300 mg, 70% yield of theory): 1H NMR (400 MHz, CDCl3) δ 6.70 (s, 1H, benzylic), 6.52 (s, 1H, benzylic), 4.23 (t, 2H, J=2.8, 1.6 Hz, ring CH2), 3.39 (t, 2H, J=4.4, 6.8 Hz, ring CH2), 1.63 (s, 4H, 2 CH2), 1.22 (s, 12H, 4 CH3).

Workup

  1. additionwas added LiA1H4 (4.6 ml, 4.6 mmol)
  2. extractionextracted with EtOAc (100 ml)
  3. dry with materialdried with anhydrous MgSO4 (0.5 g)
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-d35f7cdae9714c4aa8b29b85f85c3cff
Source dataset
uspto-grants-1998_06
Patent number
US05770378

Reaction notes

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