Ammonium Chloride → 2,2-Dimethyl-5-{1-[4-(2-methyl-benzylsulfanyl)-phenyl]-but-2-ynyl}-[1,3]dioxane-4,6-dione

HRID 1160293Notes

Reaction equation

HRID 1160293 reaction equation
[C:1]([Mg]Br)#[C:2][CH3:3].[CH3:6][C:7]1([CH3:31])[O:12][C:11](=[O:13])[C:10](=[CH:14][C:15]2[CH:20]=[CH:19][C:18]([S:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=3[CH3:29])=[CH:17][CH:16]=2)[C:9](=[O:30])[O:8]1.[NH4+].[Cl-]>C1COCC1>[CH3:6][C:7]1([CH3:31])[O:12][C:11](=[O:13])[CH:10]([CH:14]([C:15]2[CH:16]=[CH:17][C:18]([S:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=3[CH3:29])=[CH:19][CH:20]=2)[C:1]#[C:2][CH3:3])[C:9](=[O:30])[O:8]1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 591326082,2-Dimethyl-5-[4-(2-methyl-benzylsulfanyl)-benzylidene]-[1,3]dioxane-4,6-dioneHCID 178419101HCID 178419101, compound

Product 1

HCID 591326202,2-Dimethyl-5-{1-[4-(2-methyl-benzylsulfanyl)-phenyl]-but-2-ynyl}-[1,3]dioxane-4,6-dioneYield 15%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

An oven-dried 100 mL pear-shaped flask, fitted with an oven-dried stir bar, was charged with a 0.5 M solution of 1-propynyl magnesium bromide in THF (12.5 mL, 6.27 mmol) via cannula. The solution was cooled to 0° C., and then a solution of 28.2 (1.05 g, 2.85 mmol) in anhydrous THF (6 mL) was added over 3 minutes via cannula. The reaction was stirred at 0° C. for 5 minutes and then stirred at room temperature for 1.5 hours. The reaction mixture was poured into saturated NH4Cl(aq) and extracted with ethyl acetate. The combined organic layers were washed with water, followed by brine. The combined organic layers were dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified via radial chromatography (20% ethyl acetate in hexanes) followed by recrystallization from hot ethyl acetate and hexanes to yield 162 mg (15%) of 2,2-Dimethyl-5-{1-[4-(2-methyl-benzylsulfanyl)-phenyl]-but-2-ynyl}-[1,3]dioxane-4,6-dione (28.3). LC/MSD m/e: 409.1 (M+H).

Workup

  1. customAn oven-dried 100 mL pear-shaped flask, fitted with an oven-dried
  2. stirringThe reaction was stirred at 0° C. for 5 minutes
  3. stirringstirred at room temperature for 1.5 hours
  4. extractionextracted with ethyl acetate
  5. washThe combined organic layers were washed with water
  6. dry with materialThe combined organic layers were dried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customThe resulting residue was purified via radial chromatography (20% ethyl acetate in hexanes)
  9. customfollowed by recrystallization from hot ethyl acetate and hexanes

Sources & evidence

ORD record
ord-90dce07b42ea4193b3bf5521fc313997
Source dataset
uspto-grants-2010_10
Patent number
US07816367B2

Reaction notes

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