Iodine → HCID 67499143, compound

HRID 1484733Notes

Reaction equation

[CH3:1][C:2]1[CH:6]=[CH:5][N:4]([C:7]2[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=2)[N:3]=1.[I:13](O)(=O)=O.II.[S].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(O)(=O)C>[I:13][C:6]1[C:2]([CH3:1])=[N:3][N:4]([C:7]2[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=2)[CH:5]=1

Participants

Conditions

Temperature: 70 °C

Procedure

To a mixture of 3-(3-methyl-1H-pyrazol-1-yl)pyridine (6.7 g, 42.1 mmol), iodic acid (2.96 g, 16.84 mmol), and diiodine (8.55 g, 33.7 mmol) in acetic acid (60.1 ml) was added concentrated sulfur acid (3.74 ml, 21.04 mmol). The reaction mixture heated to 70° C. for 30 minutes. The reaction mixture was poured onto ice with sodium thiosulfate and was extracted with diethyl ether. The combined organic phases were washed with saturated aqueous sodium bicarbonate. The organic phases were then dried with magnesium sulfate, filtered and concentrated in vacuo. The solid residue was dissolved in dichloromethane, applied to a 80 g silica gel column, and eluted with 0-80% acetone in hexanes to afford 3-(4-iodo-3-methyl-1H-pyrazol-1-yl)pyridine (11.3 g, 35.7 mmol, 85%) as a white solid: mp 131° C.; 1H NMR (400 MHz, CDCl3) δ 8.95-8.85 (m, 1H), 8.52 (dd, J=4.8, 1.4 Hz, 1H), 8.00-7.94 (m, 1H), 7.91 (s, 1H), 7.38 (ddd, J=8.3, 4.8, 0.7 Hz, 1H), 2.34 (s, 3H); EIMS m/z 285.

Workup

extractionwas extracted with diethyl ether
washThe combined organic phases were washed with saturated aqueous sodium bicarbonate
dry with materialThe organic phases were then dried with magnesium sulfate
filtrationfiltered
concentrationconcentrated in vacuo
dissolutionThe solid residue was dissolved in dichloromethane
washeluted with 0-80% acetone in hexanes

Sources & evidence

ORD record: ord-9bcbe236df3343779fe107b39bd4a7bd
Source dataset: uspto-grants-2016_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09422278B2

Reaction notes

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