Participants
| Role | Name | HCID | Charge |
|---|
| Reactant | Hydrochloric Acid | HCID 313 | — |
| Reactant | Acetyl chloride | HCID 6367 | — |
| Reactant | Isobutyraldehyde | HCID 6561 | — |
| Reactant | Diisopropylethylamine | HCID 81531 | — |
| Reactant | Sodium triacetoxyborohydride | HCID 5049666 | — |
| Reactant | HCID 67373992 | HCID 67373992 | — |
| Catalyst | Acetic Acid | HCID 176 | — |
| Catalyst | 4-(Dimethylamino)pyridine | HCID 14284 | — |
| Solvent | Diethyl Ether | HCID 3283 | — |
| Solvent | Dichloromethane | HCID 6344 | — |
| Solvent | Water ethylacetate | HCID 22728543 | — |
| Product | HCID 67373322 | HCID 67373322 | 33.6% |
Reaction Steps
To a solution of 5-[3-butyl-6-(1-methyl-piperidin-4-yloxy)-pyridazin-4-yl]-2-cyclohexyloxy-phenylamine (Example 62, 0.2 mmol, 88 mg) in DCM (2.0 mL) was added isobutyraldehyde (0.3 mmol, 28 μL), and 1 drop of acetic acid. Then sodium triacetoxyborohydride (0.6 mmol, 127 mg) was added. The mixture was stirred at room temperature for 1 hour then condensed. The mixture was then diluted with water/EtOAc. The solvent was removed in vacuo and the residue was again dissolved in DCM (2.0 mL) at 0° C., added acetyl chloride (0.4 mmol, 29 μL), DIEA (0.6 mmol, 105 μL) and DMAP (5 mg). And the mixture was stirred at room temperature for 1 hour. It was then condensed in vacuo and the residue was purified by silica gel chromatography (DCM to DCM+10% 2N NH3 in MeOH) to give a colorless sticky solid, which was dissolved in DCM (1.0 mL), 2N HCl in ether (1.0 mL) was added, kept at room temperature for 10 min, condensed, triturated with hexanes to provide the title compound (41 mg). LCMS: m/z 537 [M+1]. 1H NMR (400 MHz, CD3OD): δ 7.40-7.43 (1H, m), 7.28-7.35 (2H, m), 7.07 (1H, s), 5.52 (1H, bs), 4.53-4.59 (1H, m), 3.65-3.71 (1H, m), 3.29-3.47 (7H, m), 2.92-2.97 (2H, m), 2.89 (3H, s), 2.18-2.37 (4H, m), 1.99-2.07 (2H, m), 1.84 (3H, s), 1.25-1.83 (9H, m), 1.18-1.26 (2H, m), 0.91-0.95 (6H, m), 0.80 (3H, t).
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
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| Patent number | US08431575B2 |
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| Source dataset | uspto-grants-2013_04 |
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| ORD ID | ord-86191449f9a343da8bd35c6830a87b72 |
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| Source note | uspto-grants-2013_04 |
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