Dimethylformamide → HCID 19827846, compound

HRID 1494359Notes

Reaction equation

HRID 1494359 reaction equation
BrC1C2C(=CC=CC=2)[C:5]([O:12]C)=C([N+]([O-])=O)C=1.Br[C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:21]([NH:28][CH:29]([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)C)=[C:20]([N+:37]([O-])=O)[CH:19]=1.[CH2:40](N(CC)CC)C.CN(C)[CH:49]=[O:50]>C(O)C.O1CCCC1.[Ni].[Pd]>[C:36]1([CH2:31][CH2:29][N:28]2[C:21]3[C:22]4[CH:23]=[CH:24][CH:25]=[CH:26][C:27]=4[CH:18]=[CH:19][C:20]=3[NH:37][C:5](=[O:12])[C:49]2=[O:50])[CH:35]=[CH:34][CH:33]=[CH:32][CH:40]=1

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 8471Triethylamine2×HCID 13806181HCID 13806181, compoundHCID 67842209HCID 67842209, compound

Product 1

HCID 19827846HCID 19827846, compoundYield 22%

Reagents, catalysts & solvents 4

HCID 935NickelCatalystHCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 4-bromo-1-methoxy-2-nitronaphthalene (2.82 g, 10 mmol) and 12.5 -phenylethylamine (1.4 ml, 11 mmol) in 20 ml of dry N,N-dimethylformamide was stirred at 80° C. for 2 h, Ni/Raney. and evaporated to dryness in vacuo. The crude 4-bromo-2-nitro-1-phenylethylaminonaphthalene (3.7 g, 10 mmol) was suspended in 100 ml of 96% ethanol. Dry triethylamine (1.4 ml, 10 mmol) was added, and the mixture was hydrogenated at room temperature and atmospheric pressure in the presence of 5% palladium-on-carbon (300 mg) for 6 h. The catalyst was filtered off, and the filtrate was evaporated to dryness. The residue was taken up in 25 ml of dry tetrahydrofuran, and dry triethylamine (1.4 ml, 10 mmol) was added. Then a solution of ethyl oxalylchloride (1.2 ml, 10 mmol) in 5 ml of dry tetrahydrofuran was added dropwise with stirring at 0° C. The mixture was stirred over night at room temperature and evaporated to dryness. The residue was triturated with 40 ml of ethanol and filtered. Washing with water and ethanol afforded 0.70 g (22%) of the title compound. M.p. 268.1° C. (DSC); IR (KBr): 1680 cm-1 ; 1H-NMR (DMSO-d6): 3.03 (distorted t,J=7 Hz, 2H, CH2), 4.56 (distorted t,J=7 Hz, 2H, NCH2), 6.80-8.20 (m, 11H, ArH), 11.8 (broad s, 1H, NH); MS (m/z): 316 (M+, 60%).

Workup

  1. customand evaporated to dryness in vacuo
  2. customwas hydrogenated at room temperature
  3. filtrationThe catalyst was filtered off
  4. customthe filtrate was evaporated to dryness
  5. stirringThe mixture was stirred over night at room temperature
  6. customevaporated to dryness
  7. customThe residue was triturated with 40 ml of ethanol
  8. filtrationfiltered
  9. washWashing with water and ethanol

Sources & evidence

ORD record
ord-8a1653f0ed784235917651ffeba68514
Source dataset
uspto-grants-1991_06
Patent number
US05026704

Reaction notes

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