Ethyl Acetate → Methyl 2-[2-methyl-4-p-tolyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl]-2-ethoxyacetate

HRID 1627897Notes

Reaction equation

HRID 1627897 reaction equation
Cl[C:2]1[C:7]([CH:8]([O:13][CH2:14][CH3:15])[C:9]([O:11][CH3:12])=[O:10])=[C:6]([CH3:16])[N:5]=[C:4]2[S:17][C:18]3[CH2:23][CH2:22][CH2:21][CH2:20][C:19]=3[C:3]=12.C(=O)([O-])[O-].[K+].[K+].[C:30]1([CH3:39])[CH:35]=[CH:34][C:33](B(O)O)=[CH:32][CH:31]=1.C(OCC)(=O)C>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:16][C:6]1[N:5]=[C:4]2[S:17][C:18]3[CH2:23][CH2:22][CH2:21][CH2:20][C:19]=3[C:3]2=[C:2]([C:33]2[CH:34]=[CH:35][C:30]([CH3:39])=[CH:31][CH:32]=2)[C:7]=1[CH:8]([O:13][CH2:14][CH3:15])[C:9]([O:11][CH3:12])=[O:10]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 79799Tolylboronic acidHCID 66603554Methyl 2-[4-chloro-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl]-2-ethoxyacetate

Product 1

HCID 49806707Methyl 2-[2-methyl-4-p-tolyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl]-2-ethoxyacetateYield 54%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 18180031Water 1,2-dimethoxyethaneSolvent

Conditions

Temperature
140 °C

Procedure

To a solution of methyl 2-[4-chloro-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl]-2-ethoxyacetate (0.040 g; 0.113 mmol) in a mixture of DME-water (3:1) (0.48 mL) were added potassium carbonate (0.062 g; 0.452 mmol), tetrakis(triphenylphosphine)palladium(0) (0.0065 g; 0.0056 mmol) and 4-tolylboronic acid (0.031 g; 0.226 mmol). The solution was stirred for 30 min at 140° C. under microwave irradiation. Ethyl acetate was added to the reaction mixture and the solution was washed with brine. The organic phase was dried over magnesium sulphate, filtered and concentrated under reduced pressure. Purification by flash chromatography on silica gel using a gradient of ethylacetate (5-40%) in heptane furnished 0.025 g (54%) of the title compound as a solid.

Workup

  1. washthe solution was washed with brine
  2. dry with materialThe organic phase was dried over magnesium sulphate
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. customPurification by flash chromatography on silica gel using a gradient of ethylacetate (5-40%) in heptane

Sources & evidence

ORD record
ord-9567b9302b63449295ef63baadaeb643
Source dataset
uspto-grants-2014_07
Patent number
US08785638B2

Reaction notes

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