Ethyl Thioglycolate → HCID 67352988, compound

HRID 1676133Notes

Reaction equation

HRID 1676133 reaction equation
[H-].[Na+].[CH2:3]([O:5][C:6](=[O:9])[CH2:7][SH:8])[CH3:4].[C:10]([C:13]([CH2:24][C:25]([CH3:27])=[CH2:26])=[C:14](OS(C(F)(F)F)(=O)=O)[CH3:15])(=O)[CH3:11].[OH-].[Na+]>CCCCC.C1COCC1.C(Cl)Cl.O>[CH2:3]([O:5][C:6]([C:7]1[S:8][C:10]([CH3:11])=[C:13]([CH2:24][C:25]([CH3:27])=[CH2:26])[C:14]=1[CH3:15])=[O:9])[CH3:4]

Participants

9

Reactant 4

HCID 12185Ethyl ThioglycolateHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 86645770HCID 86645770, compound

Product 1

HCID 67352988HCID 67352988, compoundYield 47.2%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

Sodium hydride (60% in petrolether, 404 mg, 10 mmol) is washed with dry pentane (3×10 mL), then dry THF (30 mL) is added and the suspension is cooled at 0° C. A solution of mercaptoacetic acid ethyl ester (0.445 mL, 4 mmol) in THF (4 mL) is slowly added. After stirring for 0.5 h at 0° C. a solution of trifluoromethanesulfonic acid 2-acetyl-1,4-dimethyl-penta-1,4-dienyl ester (1.16 g, 4 mmol) in THF (4 mL) is slowly added. The mixture is stirred at 0° C. for 0.5 h, then slowly warmed to rt during 15 h. The reaction mixture is partioned between H2O (75 mL) and DCM (100 mL), the aq. phase is basified with 1M aq. NaOH (50 mL) and extracted with DCM (50 mL). The combined organic extracts are dried (Na2SO4), filtered and evaporated. The crude product is purified by reversed phase MPLC (H2O-MeOH gradient) to give 450 mg of 3,5-dimethyl-4-(2-methyl-allyl)-thiophene-2-carboxylic acid ethyl ester; LC-MS: tR=1.10 min, [M+1]+=239.05.

Workup

  1. additionis slowly added
  2. temperatureslowly warmed to rt during 15 h
  3. extractionextracted with DCM (50 mL)
  4. dry with materialThe combined organic extracts are dried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude product is purified by reversed phase MPLC (H2O-MeOH gradient)

Sources & evidence

ORD record
ord-b0958d4987bf41c1b12f5c6c71dc99ff
Source dataset
uspto-grants-2011_08
Patent number
US08003800B2

Reaction notes

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