Diethyl Sulfate → HCID 15017021, compound

HRID 2099042Notes

Reaction equation

HRID 2099042 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=[C:6]([Cl:14])[C:5]=1[N:15]1[C:19]([OH:20])=[C:18]([S:21][C:22]([F:25])([F:24])[F:23])[C:17]([C:26]#[N:27])=[N:16]1.S(OCC)(O[CH2:32][CH3:33])(=O)=O.S([O-])(O)(=O)=O.[K+]>O1CCOCC1>[Cl:3][C:4]1[CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=[C:6]([Cl:14])[C:5]=1[N:15]1[C:19]([O:20][CH2:32][CH3:33])=[C:18]([S:21][C:22]([F:25])([F:23])[F:24])[C:17]([C:26]#[N:27])=[N:16]1

Participants

6

Reactant 4

HCID 6163Diethyl SulfateHCID 24758Sodium hydrideHCID 516920Potassium bisulfateHCID 178510673HCID 178510673, compound

Product 1

HCID 15017021HCID 15017021, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

To a stirred suspension of sodium hydride (0.41 g, 60%, 10.3 mmol) in dioxane (150 ml) was added a solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-5-hydroxy-4-trifluoromethylthio-1H-pyrazole-3-carbonitrile (4.00 g, 8.53 mmol) in dioxane (50 ml). After gas evolution had ceased the mixture was heated to reflux and diethyl sulfate (1.25 ml, 9.47 mmol) added, and then heated under reflux for 6 hours. The cooled mixture was acidified with aqueous potassium hydrogensulfate (5%), extracted with dichloromethane, and the organic phase dried over magnesium sulfate and evaporated. The resulting gum was triturated with pentane to give 1-(2,6-dichloro-4-trifluoromethylphenyl)-5-ethoxy-4-trifluoromethylthio-1 H-pyrazole-3-carbonitrile (2.68 g, yield 70 %) as off-white crystals, mp 106° C., 1H NMR (CDCl3): 1.36 (t, 3H, CH3), 4.71 (q, 2H, OCH2), and 7.76 (s, 2H, Ar—H).

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. temperatureheated
  4. temperatureunder reflux for 6 hours
  5. extractionextracted with dichloromethane
  6. dry with materialthe organic phase dried over magnesium sulfate
  7. customevaporated
  8. customThe resulting gum was triturated with pentane

Sources & evidence

ORD record
ord-17fa2b01a41b4027babc84fe1e804831
Source dataset
uspto-grants-2009_08
Patent number
US07569516B2

Reaction notes

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