1,3-Cyclohexanedione → HCID 11413257, compound

HRID 1057658Notes

Reaction equation

HRID 1057658 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([NH2:9])[CH:4]=1.N([O-])=O.[Na+].O.O.[Sn](Cl)Cl.[C:19]1(=O)[CH2:24][CH2:23][CH2:22][C:21](=[O:25])[CH2:20]1.[OH-].[Na+]>O.Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:6]([C:20]3[C:21](=[O:25])[CH2:22][CH2:23][CH2:24][C:19]=3[NH:9]2)=[CH:7][CH:8]=1

Participants

8

Reactant 5

HCID 104341,3-CyclohexanedioneHCID 108243-MethoxyanilineHCID 14798Sodium HydroxideHCID 61436Stannous chloride dihydrateHCID 23668193Sodium Nitrite

Product 1

HCID 11413257HCID 11413257, compoundYield 13.1%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

To a chilled mixture of m-anisidine (10 g, 81 mmol) in water (200 mL) and concentrated hydrochloric acid (25 mL) is added sodium nitrite (5.6 g, 81 mmol) dissolved in water (30 mL). The mixture is stirred at 5° C. for one h. To this is added tin (II) chloride dihydrate (36.6 g, 162 mmol) dissolved in concentrated hydrochloric acid (75 mL). The mixture is allowed to warm to room temperature and stirred for 1 h. 1,3 cyclohexanedione (9.1 g, 81 mmol) is added and the mixture stirred for 2 h. The mixture is slowly neutralized with 10% NaOH. Filtered solids and washed with water (500 mL). The solids are then slurried in acetonitrile (600 mL), filtered and washed with acetonitrile (200 mL). The filtrates are dried over anhydrous sodium sulfate, filtered and concentrated. The residue is refluxed in TFA (70 mL) for 18 h. The mixture is partitioned between water and CH2Cl2. The organic layer is separated and washed twice with water (200 mL). The organic layer is dried over anhydrous sodium sulfate, filtered, and concentrated. Ethyl acetate (100 mL) is added to the residue and the solids filtered to give 2.29 g (13%) of the title compound; IR (drift) 3156, 3118, 3073, 1620, 1583, 1501, 1470, 1451, 1288, 1196, 1178, 1153, 1142, 1107, 830 cm−1. 1H NMR (DMSO-d6) δ2.08, 2.7, 2.9, 3.8, 6.7, 6.9, 7.8; Anal. Calcd for C13H13NO2: C, 72.54; H, 6.09; N, 6.51. Found: C, 60.95; H, 5.18; N, 5.61.

Workup

  1. temperatureto warm to room temperature
  2. stirringstirred for 1 h
  3. stirringthe mixture stirred for 2 h
  4. filtrationFiltered solids
  5. washwashed with water (500 mL)
  6. filtrationfiltered
  7. washwashed with acetonitrile (200 mL)
  8. dry with materialThe filtrates are dried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. temperatureThe residue is refluxed in TFA (70 mL) for 18 h
  12. customThe mixture is partitioned between water and CH2Cl2
  13. customThe organic layer is separated
  14. washwashed twice with water (200 mL)
  15. dry with materialThe organic layer is dried over anhydrous sodium sulfate
  16. filtrationfiltered
  17. concentrationconcentrated
  18. additionEthyl acetate (100 mL) is added to the residue
  19. filtrationthe solids filtered

Sources & evidence

ORD record
ord-41e59843d9cd477f8ae17f3d0c4828e3
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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