(6-Dimethylamino-3-nitro-2-pyridyl)acetonitrile → N,N-dimethyl-1H-pyrrolo[3,2-b]pyridin-5-amine

HRID 1681278Notes

Reaction equation

HRID 1681278 reaction equation
[CH3:1][N:2]([CH3:15])[C:3]1[N:8]=[C:7]([CH2:9][C:10]#N)[C:6]([N+:12]([O-])=O)=[CH:5][CH:4]=1>[Ni].C(OCC)(=O)C>[CH3:1][N:2]([CH3:15])[C:3]1[N:8]=[C:7]2[CH:9]=[CH:10][NH:12][C:6]2=[CH:5][CH:4]=1

Participants

4

Reactant 1

HCID 14822073(6-Dimethylamino-3-nitro-2-pyridyl)acetonitrile2×

Product 1

HCID 14822069N,N-dimethyl-1H-pyrrolo[3,2-b]pyridin-5-amineYield 27.3%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of (6-dimethylamino-3-nitro-2-pyridyl)acetonitrile (Compound 5c, 2.06 g, 10.0 mmol), Raney nickel (0.70 g, washed thoroughly with absolute ethanol), and absolute ethanol/acetic acid (4:1, 50 mL) was shaken under a hydrogen atmosphere (3 atm) for 3 hours. The resulting mixture was filtered through diatomaceous earth (Celite (trademark)), and the filtrate was evaporated under reduced pressure. The residual oil was dissolved in water (25 mL), the pH was adjusted to 10 with sodium carbonate, and the mixture was extracted with methylene chloride (3×25 mL). These extracts were combined, dried (MgSO4), and evaporated under reduced pressure to yield an oil. This oil was dissolved in ethyl acetate (10 mL), and this solution was passed through an alumina (basic) filter (approximately 100 g) followed by ethyl acetate (1,500 mL). The resulting filtrate was evaporated under reduced pressure to yield Compound 7j (0.44 g, 2.73 mmol, 27%) as a white solid: mp, 149.0°-151.0° C.; IR (KBr) 1,620, 1,590, 1,505, 1,475, 1,455, 1,410 cm-1 ; 1H NMR (CDCl3) 8.68 (br m, 1H), 7.47 (d, J=8.8 Hz, 1H), 7.21 (t, J=3.0 Hz, 1H), 6.50 (d, J=8.8 Hz, 1H), 6.49-6.47 (m, 1H), 3.10 (s, 6H); 13C NMR (CDCl3) δ 156.6, 144.3, 126.4, 120.8, 102.7, 102.0, 39.3; LRMS (m/z, relative intensity) 162 (21), 161 (M+, 99), 160 (23), 146 (80), 132 (100), 119 (36), 118 (82), 117 (81), 90 (19). Anal. Calcd for C9H11N3 : C, 67.06; H, 6.88; N, 26.08; found: C, 66.69; H, 6.81; N, 25.94.

Workup

  1. washwashed thoroughly with absolute ethanol), and absolute ethanol/acetic acid (4:1, 50 mL)
  2. filtrationThe resulting mixture was filtered through diatomaceous earth (Celite (trademark))
  3. customthe filtrate was evaporated under reduced pressure
  4. dissolutionThe residual oil was dissolved in water (25 mL)
  5. extractionthe mixture was extracted with methylene chloride (3×25 mL)
  6. dry with materialdried (MgSO4)
  7. customevaporated under reduced pressure
  8. customto yield an oil
  9. filtrationfilter (approximately 100 g)
  10. customThe resulting filtrate was evaporated under reduced pressure

Sources & evidence

ORD record
ord-36383c0ccddd4f169dfa9ef5c845e965
Source dataset
uspto-grants-1992_12
Patent number
US05169947

Reaction notes

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