3-Iodo-5-nitro-2-pyridinamine

5-nitropyridin-2-amine (14 g, 10 mmol), KI (16.6 g, 10 mmol), KIOCompound 1 (0.50 g, 3.59 mmol) was dissolved in 2 M H2SO4(7.18 mL). KIO3 (0.31 g, 1.44 mmol) was slowly added at room temperature.After heating at 100 C, a solution of KI in water (1 M, 3.59 mL, 0.60 g, 3.59 mmol) was dropwise added to the reactionmixture. Heating at reflux was continued for 2 h, then the mixturewas cooled to room temperature. The mixture was adjusted to pH7.0 with the careful addition of a sat. NaHCO3 solution. It was thendiluted with EtOAc and solid sodium thiosulfate was added withvigorous stirring until the iodine coloration disappeared. A significantamount of a yellowish solid precipitated out of the solution, which was collected by filtration, washed with water and dried to give a yellow solid as a pure compound. On the other hand, the organic layer was washed with brine and evaporated to givea yellow solid as a pure compound. These combined yellow solidswere used in the next reaction without further purification. All ofthe solids totaled 0.88 g. 1H NMR (500 MHz, DMSO-d6) d (ppm)8.85 (d, J = 2.5 Hz, 1H), 8.58 (d, J = 2.5 Hz, 1H), 7.61 (brs, 1H). 13CNMR (125 MHz, DMSO-d6) d (ppm) 75.07, 134.74, 141.63, 145.75, 162.25. HRMS (ESI-TOF, m/z) Calcd. for C5H4IN3O2Na [M+Na]+:287.9246, Found: 287.9226To a solution of compound 1 (50 g, 359.71 mmol) in HPrepared in two steps from 3-iodo-5-nitropyridin-2-amine:Step 1: To a 25 mL three-necked flask charged with 5-nitropyridin-2-amine (1 g, 7.1 mmol, 1 equiv), was added concentrated sulfuric acid (12 mL, 0.6 M) and potassium iodate (653 mg, 2.8 mmol, 0.4 equiv) portionwise, before subsequent heating to 200 °C. Potassium iodide (1.18 g, 7.1 mmol, 1 equiv) was then added dropwise as an aqueous solution (4 mL), and the reaction mixture was stirred at 200 °C for 1.5 h. Upon completion, the reaction mixture was allowed to cool to room temperature before the slow addition of saturated sodium bicarbonate solution (20 mL) and EtOAc (20 mL). The reaction mixture was separated and the organics were washed with an aqueous solution of saturatedNa2S2O3 (2 × 30 mL). The organics were then passed through a hydrophobic frit and concentrated under reduced pressure to give a yellow solid, 3-iodo-5-nitropyridin-2-amine, which was used without further purification (1.64 g, 87 percent).Step 2: To a 100 mL round-bottomed flask charged with 3-iodo-5-nitropyridin-2-amine (1.29 g, 4.86 mmol, 1 equiv) was added THF (40 mL, 0.13 M) and the reaction mixture was cooled to 0 °C. Sodium hydride (224 mg, 9.72 mmol, 2 equiv) was added portionwise and the reaction mixture wasstirred at 0 °C for 20 minutes. 4-Methylbenzenesulfonyl chloride (1.09 g, 4.86 mmol, 1 equiv) was added portion wise, and the reaction mixture was allowed to slowly warm to room temperature and was stirred for 18 h. Upon completion of the reaction, water (50 mL) and CH2Cl2 (50 mL) were added and the reaction mixture was separated and the organics washed with 1 M NaOH (2 × 50 mL), 1 MHCl (2 × 50 mL), and brine (2 × 50 mL). The organics were passed through a hydrophobic frit and concentrated under reduced pressure to give a crude residue, which was purified by flash chromatography (silica gel, 0–30percent EtOAc in petroleum ether) to afford the title compound as a yellow solid (1.43 g, 70percent).max (solid): 3581, 3268, 3064, 2919, 1571, 1444, 1320 cm-1.1H NMR (DMSO-d6, 500 MHz): δ 8.66 (d, J = 2.6 Hz, 1H), 8.40 (d, J = 2.5 Hz, 1H), 7.74 (d, J = 8.1 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 3.35 (bs, 1H), 2.32 (s, 3H).13C NMR (DMSO-d6, 126 MHz): δ 161.9, 145.0, 142.3, 140.9, 140.7, 134.7, 128.9, 127.4, 86.7, 21.4.HRMS: exact mass calculated for [M+H]+(C12H11IN3O4S) requires m/z 419.9509, found m/z 419.9510.Characterisation data is consistent with literature reported values.4

The starting material for the azaindole chemical reaction.

Molecular Weight:265.01
XLogP3:1
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:4
Exact Mass:264.93482
Monoisotopic Mass:264.93482
Topological Polar Surface Area:84.7
Heavy Atom Count:11
Complexity:160
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes