Triethylamine → HCID 19827832, compound

HRID 1709234Notes

Reaction equation

HRID 1709234 reaction equation
[H][H].Cl.[NH2:4][C:5]1[C:14]2[C:9](=[CH:10][C:11]([Br:15])=[CH:12][CH:13]=2)[CH:8]=[CH:7][C:6]=1[NH:16][CH:17]1[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1.C(N(CC)CC)C.CC[C:32]([C:34](Cl)=[O:35])=[O:33]>C(O)C.O1CCCC1.[Ni]>[Br:15][C:11]1[CH:12]=[CH:13][C:14]2[C:5]3[NH:4][C:34](=[O:35])[C:32](=[O:33])[N:16]([CH:17]4[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]4)[C:6]=3[CH:7]=[CH:8][C:9]=2[CH:10]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 11007880Butanoyl chloride, 2-oxo-HCID 19827839HCID 19827839, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 19827832HCID 19827832, compound

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 6-bromo-2-methoxy-1-nitronaphthalene (10.0 g, 35.6 mmol) and 8 ml of cyclohexylamine in 50 ml of dry N,N-dimethylformamide was heated with stirring at 120° C. for 17 h. The mixture was evaporated to dryness and the residue was triturated with 50 ml of ethanol at 0° C. The solid was isolated by filtration and washed with light petroleum to give 10.4 g (84%) of 6-bromo-2-cyclohexylamino-1-nitronaphthalene. The crude product was suspended in 150 ml of 96% ethanol and hydrogenated at room temperature and 40 psi over Ni/Raney. After the hydrogen uptake was completed, the reaction mixture was filtered into 50 ml of 4M hydrochloric acid and concentrated to dryness. Crude 1-amino-6-bromo-2-cyclohexylaminonaphthalene hydrochloride (9.8 g, 27.6 mmol) was taken up in 80 ml of dry tetrahydrofuran. Dry triethylamine (7.7 ml, 55.3 mmol) was added, followed by the dropwise addition of ethyloxalyl chloride (3.1 ml, 27.7 mmol) with stirring at 0° C. The mixture was stirred over night at room temperature and finally at reflux for 4 h. The cooled mixture was filtered and the solid was washed with water and ethanol affording 5.2 g (51%) of the title compound. M.p. 347.0° C. (N,N-dimethylformamide, DSC); IR (KBr): 1700 cm-1 ; 1H-NMR (DMSO-d6) 1.13-2.93 (m, 10H, 5CH2), 4.33-4.90 (m, 1H, NCH), 7.47-8.67 (m, 5H, ArH), 12.1 (broad s, 1H, NH); MS (m/z): 372 (M+, 17%).

Workup

  1. filtrationthe reaction mixture was filtered into 50 ml of 4M hydrochloric acid
  2. concentrationconcentrated to dryness
  3. stirringThe mixture was stirred over night at room temperature
  4. temperaturefinally at reflux for 4 h
  5. filtrationThe cooled mixture was filtered
  6. washthe solid was washed with water and ethanol affording 5.2 g (51%) of the title compound

Sources & evidence

ORD record
ord-ec5115a486554aa2803b7decc627fa4f
Source dataset
uspto-grants-1990_08
Patent number
US04948794

Reaction notes

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