Participants
| Role | Name | HCID | Charge |
|---|
| Reactant | Acetic Acid | HCID 176 | — |
| Reactant | Formaldehyde | HCID 712 | — |
| Reactant | Sodium triacetoxyborohydride | HCID 5049666 | — |
| Reactant | 2-Chloro-5-iodopyridin-4-amine | HCID 45480366 | — |
| Solvent | Water | HCID 962 | — |
| Solvent | Dichloromethane | HCID 6344 | — |
| Solvent | Sodium Bicarbonate | HCID 516892 | — |
| Product | HCID 89561302 | HCID 89561302 | 100% |
Reaction Steps
A mixture of 2-chloro-5-iodopyridin-4-amine (262 mg, 1.03 mmol), excess paraformaldehyde (618 mg, 21 mmol) and AcOH (10.3 mL) was stirred at 40° C. for 15 minutes, followed by addition of excess sodium triacetoxyborohydride (4.8 g, 23 mmol). After stirring for 2.5 hours, further paraformaldehyde (236 mg, 7.86 mmol) and sodium triacetoxyborohydride (1.83 g, 8.63 mmol) were added. After 18 hours, the mixture was diluted with water and basified with NaHCO3. The mixture was extracted with EtOAc (3×30 mL). The combined organic extracts were dried and evaporated onto silica. Gradient chromatography, eluting with 5-10% EtOH: CH2Cl2 over 17 column volume, gave 2-chloro-N-ethyl-5-iodopyridin-4-amine (291 mg, 1.03 mmol, 100% yield). LC-MS (LCT, 3.5 minutes) Rt=2.56 minutes; m/z (ESI) 282 (M+H). The material was reacted with 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole following General Procedure i to give 2-chloro-N-ethyl-5-(1-methyl-1H-pyrazol-4-yl)pyridin-4-amine.
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
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| Patent number | US09040540B2 |
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| Source dataset | uspto-grants-2015_05 |
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| ORD ID | ord-fd48348bd2a941c9be2a310a30d78924 |
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| Source note | uspto-grants-2015_05 |
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