Potassium Carbonate → Diethyl 4-(4-methyl-4-(methyldisulfanyl)pentyloxy)pyridine-2,6-dicarboxylate

HRID 58005Notes

Reaction equation

HRID 58005 reaction equation
CC1C=CC(S([O:11][CH2:12][CH2:13][CH2:14][C:15]([CH3:20])([S:17][S:18][CH3:19])[CH3:16])(=O)=O)=CC=1.O[C:22]1[CH:27]=[C:26]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[N:25]=[C:24]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:23]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[CH3:20][C:15]([S:17][S:18][CH3:19])([CH3:16])[CH2:14][CH2:13][CH2:12][O:11][C:22]1[CH:23]=[C:24]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[N:25]=[C:26]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH:27]=1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 866712794-Methyl-4-(methyldisulfanyl)pentyl 4-methylbenzenesulfonateHCID 178469316HCID 178469316, compound

Product 1

HCID 86671278Diethyl 4-(4-methyl-4-(methyldisulfanyl)pentyloxy)pyridine-2,6-dicarboxylateYield 52.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

To a stirred solution of 4-methyl-4-(methyldisulfanyl)pentyl 4-methylbenzenesulfonate (5c) (0.48 g, 1.435 mmol) and diethyl 4-hydroxypyridine-2,6-dicarboxylate (5a)(0.343 g, 1.435 mmol) in anhydrous dimethylformamide (6.5 mL) was added Potassium carbonate (0.297 g, 2.152 mmol). The reaction was stirred at 90° C. for 18 hours. Then allowed to cool to ambient temperature and quenched with saturated ammonium chloride. The mixture was extracted three times with ethyl acetate. The extracts were dried with anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Purification by silica gel chromatography (30% hexanes/ethyl acetate) yielded diethyl 4-(4-methyl-4-(methyldisulfanyl)pentyloxy)pyridine-2,6-dicarboxylate (5d)(300 mg, 52%); 1H NMR (400 Hz, CDCl3): δ 7.70 (s, 2H), 4.40 (q, 4H, J=7.2, 14.4 Hz), 4.07 (t, 2H, J=6. Hz), 2.35 (s, 3H), 1.86 (m, 2H), 1.70 (m, 2H), 1.38 (t, 6H, J=7.2 Hz), 1.27 (s, 6H); MS (m/z). found 424.1 (M+Na), 440.1 (M+K). See FIG. 5.

Workup

  1. temperatureto cool to ambient temperature
  2. customquenched with saturated ammonium chloride
  3. extractionThe mixture was extracted three times with ethyl acetate
  4. dry with materialThe extracts were dried with anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customPurification by silica gel chromatography (30% hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-f8d21da8341a403c868885d201716fc0
Source dataset
uspto-grants-2016_09
Patent number
US09434748B2

Reaction notes

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