tert-Butyl acetate → t-Butyl [4-(1-methylpiperidin-4-ylidene)-4,10-dihydro-9-oxa-3-thiabenzo[f]azulen-2-yl]acetate

HRID 389035Notes

Reaction equation

HRID 389035 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[C:10]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:12])[CH3:11].CC(C1C=CC=C(C(C)C)C=1N1C=[N+](C2C(C(C)C)=CC=CC=2C(C)C)CC1)C.[Cl-].Br[C:49]1[S:58][C:57]2[C:56](=[C:59]3[CH2:64][CH2:63][N:62]([CH3:65])[CH2:61][CH2:60]3)[C:55]3[CH:66]=[CH:67][CH:68]=[CH:69][C:54]=3[O:53][CH2:52][C:51]=2[CH:50]=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].O>[CH3:65][N:62]1[CH2:63][CH2:64][C:59](=[C:56]2[C:55]3[CH:66]=[CH:67][CH:68]=[CH:69][C:54]=3[O:53][CH2:52][C:51]3[CH:50]=[C:49]([CH2:11][C:10]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[S:58][C:57]2=3)[CH2:60][CH2:61]1

Participants

7

Reactant 4

HCID 10908tert-Butyl acetateHCID 13838HexamethyldisilazaneHCID 27349181,3-Bis(2,6-diisopropylphenyl)-4,5-dihydro-1H-imidazol-3-ium chlorideHCID 684935954-(2-Bromo-10H-9-oxa-3-thiabenzo[f]azulen-4-ylidene)-1-methyl-piperidine

Product 1

HCID 86649445t-Butyl [4-(1-methylpiperidin-4-ylidene)-4,10-dihydro-9-oxa-3-thiabenzo[f]azulen-2-yl]acetateYield 43.1%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 962WaterSolvent

Procedure

Hexamethyldisilazane (11.97 g, 74.2 mmol) was ice-cooled in an argon atmosphere, and a 1.6 mol/L n-butyllithium-hexane solution (46.6 mL, 74.6 mmol) was added dropwise thereto. t-Butyl acetate (4.9 mL, 36.7 mmol) was added dropwise to the solution, and the mixture was stirred for 30 minutes. Pd(dba)2 (1.05 g, 1.8 mmol), N,N′-(2,6-diisopropylphenyl)dihydroimidazolium chloride (0.80 g, 1.9 mmol), and the compound obtained in Example 27 (7.0 g, 18.6 mmol) were added thereto, and the mixture was heated to room temperature, and stirred overnight. Water was added to the reaction mixture, and the product was extracted with ethyl acetate and dried over anhydrous sodium sulfate. The organic layer was distilled off under a reduced pressure, and the residue was purified by column chromatography (hexane:ethyl acetate=9:1), to give 3.30 g (43%) of the captioned compound in the form of an oily product.

Workup

  1. temperaturecooled in an argon atmosphere
  2. additiona 1.6 mol/L n-butyllithium-hexane solution (46.6 mL, 74.6 mmol) was added dropwise
  3. stirringstirred overnight
  4. extractionthe product was extracted with ethyl acetate
  5. dry with materialdried over anhydrous sodium sulfate
  6. distillationThe organic layer was distilled off under a reduced pressure
  7. customthe residue was purified by column chromatography (hexane:ethyl acetate=9:1)

Sources & evidence

ORD record
ord-688fa2ae19c449e0a4aa2dc3c2586379
Source dataset
uspto-grants-2013_02
Patent number
US08377967B2

Reaction notes

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