Participants
| Role | Name | HCID | Charge |
|---|
| Reactant | Piperidine | HCID 8082 | — |
| Reactant | 3-Acetylpyridine | HCID 9589 | — |
| Reactant | Stannous Chloride | HCID 24479 | — |
| Reactant | Pyrrolidine | HCID 31268 | — |
| Reactant | Diisopropylethylamine | HCID 81531 | — |
| Reactant | 4,6-Dichloro-2-methyl-5-nitropyrimidine | HCID 83192 | — |
| Reactant | HCID 18511064 | HCID 18511064 | — |
| Catalyst | Titanium Tetrachloride | HCID 24193 | — |
| Solvent | Dimethylformamide | HCID 6228 | — |
| Solvent | Triethylamine | HCID 8471 | — |
| Product | HCID 178423289 | HCID 178423289 | 3% |
Reaction Steps
Using the method described in Example 30 by employing 3-(1-pyrrolidinylvinyl)pyridine (freshly prepared before use from 3-acetylpyridine (Aldrich Chemical Company), pyrrolidine and TiCl4 (1.95 g, 11.2 mmol), 2-methyl-4,6-dichloro-5-nitropyrimidine (Example 76(b)) (2.32 g, 11.2 mmol), N,N-diisopropylethylamine (2.0 mL, 11.2 mmol), piperidine (1.8 mL, 17.9 mmol), NEt3 (2.5 mL) and SnCl2 (34 mL of a 2 M soln in DMF). In this example the SnCl2 solution was added to the reaction mixture at 140° C. The mixture was stirred at 140° C. for an additional 0.5 h then the heating was discontinued and the mixture was allowed to cool to room temperature. The mixture was stirred at room temperature an additional 4 d. The residue was purified by flash chromatography on silica gel with 95:5 CHCl3/MeOH as eluant to give 0.90 mg (3%) of 2-methyl-4-piperidyl-6-(3-pyridyl)pyrrolo[3,2-d]pyrimidine as a beige colored solid. This compound (89 mg, 0.30 mmol) was dissolved in 10:1 EtOAc/MeOH (10 mL) and heated to boiling. To the hot solution was added 1 M ethereal HCl (0.30 mL, 0.30 mmol). The solution was allowed to cool to room temperature. The resulting crystals were collected by filtration, washed with EtOAc (2×5 mL), Et2O (3×5 mL) and dried under vacuum at 60° C. to give 54 mg (2%) of the title compound as a brown colored solid. Mp: >280° C. 1H NMR (DMSO-d6; 500 MHz): δ 1.65 (br s, 6), 2.51 (s, 3), 4.02 (t, 4, J=5.4), 6.96 (s, 1), 7.52 (dd, 1, J=7.9, 7.9), 8.32 (d, 1, J=8.0), 8.61 (d, 1, J=4.8), 9.11 (d, 1, J=2.1), 12.08 (s, 1), 14.29 (s, 1). MS m/z: 294 (M+1 for free base). Anal. Calcd for C17H19N5.1.05HCl.1.5H2O: C, 56.90; H, 6.48; N, 19.52; Cl, 10.37. Found: C, 57.20; H, 6.23; N, 19.50; Cl, 10.39.
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
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| Patent number | US06187777B1 |
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| Source dataset | uspto-grants-2001_02 |
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| ORD ID | ord-f290838eacf442fbbf7b998905e16684 |
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| Source note | uspto-grants-2001_02 |
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