Hydrochloric Acid → HCID 60060166, compound

HRID 1838307Notes

Reaction equation

HRID 1838307 reaction equation
[CH2:1]([O:3][C:4](=[O:21])[CH:5]([C:11]1[C:16]([N+:17]([O-:19])=[O:18])=[CH:15][CH:14]=[C:13]([Cl:20])[N:12]=1)C(OCC)=O)[CH3:2].[Li+].[Cl-].CS(C)=O.Cl>O>[CH2:1]([O:3][C:4](=[O:21])[CH2:5][C:11]1[C:16]([N+:17]([O-:19])=[O:18])=[CH:15][CH:14]=[C:13]([Cl:20])[N:12]=1)[CH3:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 679Dimethyl SulfoxideHCID 433294Lithium ChlorideHCID 10663245HCID 10663245, compound

Product 1

HCID 60060166HCID 60060166, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
120 °C

Procedure

A mixture of 2-(6-Chloro-3-nitro-pyridin-2-yl)-malonic acid diethyl ester (32.45 g, 103 mmol), LiCl (16.18 g, 268 mmol), H2O (10 mL), and dimethyl sulfoxide (50 mL) is stirred at 120° C. for a period of 24 h. The mixture is cooled to room temperature and diluted with H2O (400 mL). 1 N HCl (aq.) is added until all of the solids are dissolved. The mixture is extracted with EtOAc (5×150 mL), and the combined organic extracts washed with H2O (2×100 mL), then brine (100 mL), and dried over Na2SO4. The mixture is filter to remove the solids, concentrated, and purified by flash chromatography on silica (elute with 5% EtOAc in hexanes) to give the title compound as a yellow oil: 1H NMR (400 MHz, CDCl3) δ 8.39 (d, 1H, J=8.7 Hz), 7.47 (d, 1H, J=8.7 Hz), 4.28 (s, 2H), 4.19 (q, 2H, J=7.1 Hz), 1.27 (t, 3H, J=7.1 Hz); 13C (100 MHz, CDCl3) δ 168.7, 166.8, 154.8, 151.4, 135.9, 124.4, 61.7, 41.9, 14.3; MS (CI) m/z 255.2 (M+1).

Workup

  1. temperatureThe mixture is cooled to room temperature
  2. dissolutionare dissolved
  3. extractionThe mixture is extracted with EtOAc (5×150 mL)
  4. washthe combined organic extracts washed with H2O (2×100 mL)
  5. dry with materialbrine (100 mL), and dried over Na2SO4
  6. filtrationThe mixture is filter
  7. customto remove the solids
  8. concentrationconcentrated
  9. custompurified by flash chromatography on silica (elute with 5% EtOAc in hexanes)

Sources & evidence

ORD record
ord-d9dfe820f8004ee7a2202a575aeb54dd
Source dataset
uspto-grants-2004_01
Patent number
US06673811B1

Reaction notes

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