Water → 2-(2-Tert-butylphenoxy)-6-chloro-3-nitropyridine

HRID 555414Notes

Reaction equation

HRID 555414 reaction equation
CC1C=C(C)C=C(C)N=1.[C:10]([C:14]1[CH:30]=[CH:29][CH:28]=[CH:27][C:15]=1[O:16][C:17]1[N:22]=[C:21](O)[CH:20]=[CH:19][C:18]=1[N+:24]([O-:26])=[O:25])([CH3:13])([CH3:12])[CH3:11].O.P(Cl)(Cl)([Cl:34])=O>>[C:10]([C:14]1[CH:30]=[CH:29][CH:28]=[CH:27][C:15]=1[O:16][C:17]1[C:18]([N+:24]([O-:26])=[O:25])=[CH:19][CH:20]=[C:21]([Cl:34])[N:22]=1)([CH3:13])([CH3:12])[CH3:11]

Participants

5

Reactant 4

HCID 962WaterHCID 79532,4,6-TrimethylpyridineHCID 24813Phosphorus oxychlorideHCID 178440819HCID 178440819, compound

Product 1

HCID 598574142-(2-Tert-butylphenoxy)-6-chloro-3-nitropyridineYield 77%

Conditions

Temperature
130 °C

Procedure

2,4,6-Trimethylpyridine (1.6 mL) was added dropwise into 136a (2.32 g, 8.0 mmol) in phosphorus oxychloride (3.2 mL) at 0° C. The reaction mixture was heated at 130° C. for 20 h. The reaction was stopped at ˜70% conversion as determined by HPLC. The dark brown solution was poured into water (40 mL) with stirring, and stirred for 15 min. The brown precipitate was filtered, air dried, and purified by SiO2 chromatography (120 g), loaded with a CH2Cl2 and eluted using a gradient of ethyl acetate in hexanes to afford 136b (1.91 g, 77% yield) as an amber colored oil; HPLC purity 100%, 3.95 min (Method A); 1H NMR (500 MHz, CDCl3) δ ppm 8.36 (d, 1H, J, J=10.0 Hz), 7.47 (d, 1H, J=5.0 Hz), 7.23 (m, 2H), 7.16 (d, 1H, J=10.0 Hz), 6.95 (d, 1H, J=10.0 Hz), 1.36 (s, 9H); 13C (125 MHz, CDCl3) δ (ppm), 155.30, 153.23, 150.87, 141.45, 137.72, 133.22, 127.59, 126.91, 125.79, 123.04, 118.39, 34.60, 30.25.

Workup

  1. stirringstirred for 15 min
  2. filtrationThe brown precipitate was filtered
  3. customair dried
  4. custompurified by SiO2 chromatography (120 g)
  5. washeluted

Sources & evidence

ORD record
ord-1798764c9fdb47d1b7f92b1f080b3d6d
Source dataset
uspto-grants-2011_11
Patent number
US08053450B2

Reaction notes

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