Nitric Acid → HCID 19827845, compound

HRID 1494358Notes

Reaction equation

HRID 1494358 reaction equation
[N+:1]([O-:4])(O)=[O:2].[C:5]([C:7]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[C:10]([O:17][CH3:18])=[CH:9][CH:8]=1)#[N:6].S(=O)(=O)(O)O>C(OC(=O)C)(=O)C>[C:5]([C:7]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[C:10]([O:17][CH3:18])=[C:9]([N+:1]([O-:4])=[O:2])[CH:8]=1)#[N:6]

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 800634-Methoxy-1-naphthonitrile

Product 1

HCID 19827845HCID 19827845, compoundYield 77%

Reagents, catalysts & solvents 2

HCID 7918Acetic AnhydrideCatalystHCID 7918Acetic AnhydrideSolvent

Procedure

A solution of 100% nitric acid (0.91 ml, 22 mmol) in 8 ml of acetic anhydride was added dropwise to a solution of 1-cyano-4-methoxynaphthalene (3.66 g, 20 mmol) in 50 ml of acetic anhydride containing two drops of conc. sulfuric acid while maintaining the temperature at -30° to -40° C. The mixture was stirred for an additional 10 min. and filtered. The solid was washed with water and dried to give 3.5 g (77%) of 4-cyano-1-methoxy-2-nitronaphthalene. The crude product was dissolved in a mixture of 25 ml of tetrahydrofuran and 10 ml of N,N-dimethylformamide. Then 5 ml of cyclohexylamine was added, and the mixture was stirred at room temperature for 2 h. The mixture was evaporated to dryness, and the residue was triturated with light petroleum to give 4.5 g (90%) of 4-cyano-1-cyclohexylamino-2-nitronaphthalene. The crude product, suspended in 200 ml of 96% ethanol, was hydrogenated at room temperature and atmospheric pressure in the presence of 5% palladium-on-carbon. When the theoretical amound of hydrogen was taken up, the catalyst was filtered off, and the filtrate was evaporated to dryness. The resulting diaminonaphthalene was immediately suspended in a mixture of 20 ml of dry tetrahydrofuran and dry triethylamine (1.95 ml, 14 mmol). Then a solution of ethyl oxalylchloride (1.56 ml, 14 mmol) in 10 ml of dry tetrahydrofuran was added dropwise with stirring at 0 ° C. The mixture was stirred at room temperature over night, and then heated at reflux for 1 h. The cooled mixture was filtered, and the solid was washed with tetrahydrofuran and water. Recrystallization from 2-methoxyethanol afforded 1.84 g (41%) of the title compound. M.p. >300° C.; IR (KBr): 2220, 1700 cm-1 ; 1H-NMR (DMSO-d6): 0.93-4.77 (m, 11H, cyclohexyl), 7.97-8.63 (m, 5H, ArH), 11.8 (broad s, 1H, NH); MS (m/z): 319 (M+, 16%).

Workup

  1. temperaturewhile maintaining the temperature at -30° to -40° C
  2. filtrationfiltered
  3. washThe solid was washed with water
  4. customdried

Sources & evidence

ORD record
ord-cac95bde525b427db2088d1459da8e5a
Source dataset
uspto-grants-1991_06
Patent number
US05026704

Reaction notes

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