Triethylamine → Ethyl 3-[4-(1-methylpiperidin-4-ylidene)-9,10-dihydro-4H-3-thiabenzo[f]azulen-2-yl]acrylate

HRID 389020Notes

Reaction equation

HRID 389020 reaction equation
C(N(CC)CC)C.[C:8]([O:12][CH2:13][CH3:14])(=[O:11])[CH:9]=[CH2:10].C1(C)C(C(P(C(C2C(C)=CC=CC=2)=O)C(C2C(C)=CC=CC=2)=O)=O)=CC=CC=1.Br.Br[C:45]1[S:54][C:53]2[C:52](=[C:55]3[CH2:60][CH2:59][N:58]([CH3:61])[CH2:57][CH2:56]3)[C:51]3[CH:62]=[CH:63][CH:64]=[CH:65][C:50]=3[CH2:49][CH2:48][C:47]=2[CH:46]=1.[Cl-].[NH4+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C=O)C>[CH3:61][N:58]1[CH2:59][CH2:60][C:55](=[C:52]2[C:51]3[CH:62]=[CH:63][CH:64]=[CH:65][C:50]=3[CH2:49][CH2:48][C:47]3[CH:46]=[C:45]([CH:10]=[CH:9][C:8]([O:12][CH2:13][CH3:14])=[O:11])[S:54][C:53]2=3)[CH2:56][CH2:57]1

Participants

8

Reactant 5

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 25517Ammonium ChlorideHCID 19696886Tri(o-toluoyl)phosphineHCID 684884902-Bromo-4-(1-methylpiperidin-4-ylidene)-9,10-dihydro-4H-3-thiabenzo[f]azulene hydrobromide

Product 1

HCID 68489717Ethyl 3-[4-(1-methylpiperidin-4-ylidene)-9,10-dihydro-4H-3-thiabenzo[f]azulen-2-yl]acrylateYield 79%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

Triethylamine (35.5 mL, 255 mmol), ethyl acrylate (26.8 mL, 246 mmol), palladium acetate (0.4 g, 1.8 mmol), and tri(o-toluoyl)phosphine (1.5 g, 5.0 mmol) were added to a DMF (160 mL) solution of Compound 2 (9.2 g, 24.5 mmol), and the mixture was stirred overnight at 80° C. in an argon atmosphere. A saturated aqueous ammonium chloride solution was added to the reaction mixture, the product was extracted with ethyl acetate, and the organic layer was then washed with a saturated sodium chloride solution and dried over anhydrous sodium sulfate. The solvents were distilled off under a reduced pressure, and the resulting residue was then purified by column chromatography (chloroform-methanol=9:1), to give 7.6 g (79%) of the captioned compound in the form of white crystals.

Workup

  1. extractionthe product was extracted with ethyl acetate
  2. washthe organic layer was then washed with a saturated sodium chloride solution
  3. dry with materialdried over anhydrous sodium sulfate
  4. distillationThe solvents were distilled off under a reduced pressure
  5. customthe resulting residue was then purified by column chromatography (chloroform-methanol=9:1)

Sources & evidence

ORD record
ord-aed14948fe564fcfae3708f3279ecee8
Source dataset
uspto-grants-2013_02
Patent number
US08377967B2

Reaction notes

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