Nitric Acid → HCID 67264820, compound

HRID 1041773Notes

Reaction equation

HRID 1041773 reaction equation
[N+:1]([O-:4])(O)=[O:2].[CH3:5][C:6]1([CH3:17])[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH2:9][CH2:8][C:7]1=[O:16].[OH-].[K+]>>[CH3:5][C:6]1([CH3:17])[C:15]2[C:10](=[CH:11][C:12]([N+:1]([O-:4])=[O:2])=[CH:13][CH:14]=2)[CH2:9][CH2:8][C:7]1=[O:16]

Participants

4

Reactant 3

HCID 944Nitric AcidHCID 14797Potassium HydroxideHCID 360103820027-76-3

Product 1

HCID 67264820HCID 67264820, compound

Procedure

To 100 mL of HNO3 (90%) at −30° C. was slowly added 12 g 1,1-dimethyl-3,4-dihydronaphthalen-2(1H)-one (Ref.: J. Am. Chem. Soc. (1993), 115, 10628). The mixture was stirred for 10 minutes and slowly poured onto 600 mL of ice water containing 120 g of KOH (more ice was added as necessary to keep the mixture cool). The mixture was extracted with ethyl acetate, dried with sodium sulfate, filtered and concentrated in vacuo. The isomers were separated iterative silica gel column using 20% ethyl acetate in hexanes followed by trituration with ethyl ether to provide 3.8 g of the higher Rf 1,1-dimethyl-6-nitro-3,4-dihydronaphthalen-2(1H)-one: 1H NMR (300 MHz, CDCl3) δ 8.1 (dd, 1H, C7-H), 8.0 (d, 1H, C5-H), 7.5 (d, 1H, C8-H), 3.2 (t, 2H), 2.7 (t, 2H), 1.5 (s, 6H), and 5.1 g of the lower Rf 1,1-dimethyl-7-nitro-3,4-dihydronaphthalen-2(1H)-one: 1H NMR (300 MHz, CDCl3) δ 8.2 (d, 1H, C8-H), 8.0 (dd, 1H, C6-H), 7.3 (d, 1H, C5-H), 3.2 (t, 2H), 2.7 (t, 2H), 1.5 (s, 6H).

Workup

  1. customat −30° C.
  2. additionwas added as necessary
  3. temperaturecool)
  4. extractionThe mixture was extracted with ethyl acetate
  5. dry with materialdried with sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe isomers were separated iterative silica gel column

Sources & evidence

ORD record
ord-edecd178a8fe4083a8cb7c2b8794bd3e
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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