2-(TERT-BUTOXYCARBONYLAMINO)PYRIDINE

General procedure: Amine (1 mmol) and di-tert-butyl dicarbonate [(Boc)2O] (1.1 mmol) were placed in a microwave reaction vial. The LG microwave oven MG 555f was programmed to 300 W at 100 °C. The reaction was monitored using TLC. After the reaction, ice water was added to the reaction mixture which resulted in the precipitation of the product. The solid product was merely filtered off and washed with excess cold water. The product was pure enough for all practical purposes. For characterization purpose, it was further purified by column chromatography (Neutral Alumina as adsorbent, solvent system: Hexane: Ethyl acetate (7.5:2.5)).#10;To 2-aminopyridine (100 mg, 1.06 mmol) was added a solution of Boc2O (270 μL, 1.17 mmol)in t-BuOH (8.5 mL) under argon atmosphere. After stirring at rt for 3.5 h, the mixture was concentrated by rotary evaporation to afford the crude product as a light yellow solid.Purification by column chromatography (5:1 → 3:1 → 1:1 hexanes/EtOAc) yielded S1u (187mg, 91percent) as a white solid.General procedure: Boc2O (1.0 mmol) was added to a mixture of phenol or amine (1.0 mmol) andMgBr2 · OEt2 (0.1 mmol) in a round-bottom flask, at which point an evolution of gas occurs, and the reaction mixture was stirred magnetically at room temperature (ifnecessary, reactions was heated to∼60 °C). After complete consumption of the phenolor amine (by thin-layer chromatography, TLC; 3–16 h), the reaction mixture wasdiluted with water and extracted with EtOAc (3 × 20mL), and the combined EtOAcextracts were dried with Na2SO4 and concentrated under vacuum rotary evaporation.The residue was isolated by column chromatography through a bed of silicagel and eluted with 5–30percent ethyl acetate in hexane to afford the desired Bocprotectedproduct.Reference Example 80 Step 1 : fert-Butyl pyridin-2-ylcarbamate (9a)To a solution of (Boc)To the single-mouth bottle was added t-butanol (100 ml) and di-tert-butyl dicarbonate (51 g, 233.8 mmol).2-Aminopyridine (20 g, 212.5 mmol) was slowly added at room temperature and allowed to react at room temperature overnight.The reaction was monitored by spotting, and ethyl acetate (250 ml) was added, and water (100 ml) was extracted.The organic layer was washed with brine, dried over anhydrous magnesium sulfateResidue column chromatography (eluent is ethyl acetate: petroleum ether = 1:5 (v/v))Purified to 13g white solid, The yield was 31.5percent.A solution of Boc-protected 2-pyridinamine (1.0 g, 5.15 mmol, 1.0 equiv.) in 15 mL DMF was cooled to 0 C (icebath). Sodium hydride (60% suspension in oil, 259.7 mg, 6.49 mmol, 1.26 equiv.) was added portion wisemaintaining the internal temperature below 5C (ice bath). The suspension was stirred vigorously for anadditional 20 minutes at 5 C before ethyl iodide (921.5 mg, 5.91 mmol, 1.15 equiv.) was added dropwise over15 minutes. After stirring for 30 minutes, the reaction mixture was allowed to warm to r.t. over 1 h until TLCindicated full conversion. Afterwards, 25 mL water and 150 mL diethyl ether were added, the organic layerseparated and extracted with water (15 mL), saturated aqueous sodium bicarbonate solution (15 mL), andbrine (15 mL). The organic phase was dried over sodium sulfate and concentrated under reduced pressure, giving 1.25 g crude material. After purification by column chromatography (LP/EA 8:1, 40g silica) Boc-protectedproduct 6 (308.1 mg, 1.39 mmol, 27%) was isolated. [1H-NMR (400 MHz, CDCl3) delta = 8.38 (dd, J=6.0, 3.4 Hz, 1H, C6), 7.68 - 7.47 (m, 2H, C3, C5), 7.10 - 6.86 (m, 1H, C4), 3.98 (q, J=7.1 Hz, 2H, CH2), 1.52 (s, 9H, Boc), 1.23 (t, J=7.0 Hz, 3H, CH3) ppm. Spectroscopical data were in accordance with literature.] 7

Molecular Weight:194.23
XLogP3:2
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:194.105527694
Monoisotopic Mass:194.105527694
Topological Polar Surface Area:51.2
Heavy Atom Count:14
Complexity:199
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes