Ammonia → HCID 46449, compound

HRID 1910601Notes

Reaction equation

HRID 1910601 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[C:9]2[C:4]=1[CH2:5][CH2:6][CH2:7][C:8]2=O.[NH3:16].C(O)C.[BH4-].[Na+]>CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[C:9]2[C:4]=1[CH2:5][CH2:6][CH2:7][CH:8]2[NH2:16]

Participants

6

Reactant 4

HCID 222AmmoniaHCID 702EthanolHCID 705463,4-Dihydro-5,8-dimethoxynaphthalen-1(2H)-oneHCID 4311764Sodium borohydride

Product 1

HCID 46449HCID 46449, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 11026Titanium isopropoxideCatalyst

Conditions

Temperature
0 °C

Procedure

3,4-Dihydro-5,8-dimethoxynaphthalen-1(2H)-one (5 g, 24.2 mmol), titanium(IV) isopropoxide (14.2 mL, 48.5 mmol) and 2 M solution of ammonia in ethanol (60.6 mL, 121.2 mmol) were stirred at room temperature for 6 h. The reaction was cooled to 0° C. and sodium borohydride was added portionwise during 10 min (1.4 g, 36.4 mmol); the resultant mixture was stirred at rt for an additional 3 h. The reaction was quenched by pouring it into ammonium hydroxide (2 M, 60 mL), the precipitate that formed was filtered off and washed with ethyl acetate (15 mL×3). The organic layer was separated and the remaining aqueous layer was extracted with ethyl acetate (15 mL×2). The combined organic extracts were washed with 1 M HCl (25 mL). The acidic aqueous extracts were washed with ethyl acetate (50 mL), then treated with aqueous sodium hydroxide (2 M) to pH 10-12, and extracted with ethyl acetate (40 mL×3). The combined organic extracts were washed with brine, dried (Na2SO4), and concentrated in vacuo to afford 1,2,3,4-tetrahydro-5,8-dimethoxynaphthalen-1-amine as an oil (4.68 g, 93% yield). 1H NMR (400 MHz, CDCl3) δ 6.66 (s, 2H), 4.18 (br tr, 1H), 3.82 (s, 3H), 3.77 (s, 3H), 2.85-2.79 (m, 1H), 2.47-2.38 (m, 1H), 1.90-176 (m, 6H).

Workup

  1. customThe reaction was quenched
  2. additionby pouring it into ammonium hydroxide (2 M, 60 mL)
  3. customthe precipitate that formed
  4. filtrationwas filtered off
  5. washwashed with ethyl acetate (15 mL×3)
  6. customThe organic layer was separated
  7. extractionthe remaining aqueous layer was extracted with ethyl acetate (15 mL×2)
  8. washThe combined organic extracts were washed with 1 M HCl (25 mL)
  9. washThe acidic aqueous extracts were washed with ethyl acetate (50 mL)
  10. additiontreated with aqueous sodium hydroxide (2 M) to pH 10-12
  11. extractionextracted with ethyl acetate (40 mL×3)
  12. washThe combined organic extracts were washed with brine
  13. dry with materialdried (Na2SO4)
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d7ba5c33492b43c4827c804d7faed9c8
Source dataset
uspto-grants-2013_12
Patent number
US08604021B2

Reaction notes

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