Lithium Chloride → Methyl 3-acetyl-6-(benzenesulphonylmethyl)-2-methoxybenzoate

HRID 2177730Notes

Reaction equation

HRID 2177730 reaction equation
[C:1]1([S:7]([CH2:10][C:11]2[C:16]([C:17]([O:19][CH3:20])=[O:18])=[C:15]([O:21][CH3:22])[C:14](Br)=[CH:13][CH:12]=2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:24]([O:26]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:25].[Cl-].[Li+]>O1CCOCC1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:24]([C:14]1[C:15]([O:21][CH3:22])=[C:16]([C:11]([CH2:10][S:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)(=[O:9])=[O:8])=[CH:12][CH:13]=1)[C:17]([O:19][CH3:20])=[O:18])(=[O:26])[CH3:25]

Participants

6

Reactant 3

HCID 433294Lithium ChlorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 66685730Methyl 6-(benzenesulfonylmethyl)-3-bromo-2-methoxybenzoate2×

Product 1

HCID 67107631Methyl 3-acetyl-6-(benzenesulphonylmethyl)-2-methoxybenzoate

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of methyl 6-(benzenesulphonylmethyl)-3-bromo-2-methoxybenzoate (Intermediate 65, 1.0 g), 1-ethoxyvinyl tributyl stannane (0.9 ml), tetrakis-(triphenylphosphine) palladium (0.29 g) and lithium chloride (1.0 g) in dioxane (15 ml) was stirred and heated in the microwave at 150° C. for 15 minutes. The solution was filtered and the filtrate was diluted with 1M hydrochloric acid and then stirred at room temperature for 5 hours. The resultant mixture was extracted with DCM, dried (MgSO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 0-75% to give methyl 3-acetyl-6-(benzenesulphonylmethyl)-2-methoxybenzoate (0.965 g) as an oil.

Workup

  1. filtrationThe solution was filtered
  2. additionthe filtrate was diluted with 1M hydrochloric acid
  3. stirringstirred at room temperature for 5 hours
  4. extractionThe resultant mixture was extracted with DCM
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customThe filtrate was evaporated to dryness
  8. customthe residue was purified by chromatography on silica
  9. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 0-75%

Sources & evidence

ORD record
ord-9e469a49cc35437c80c570a18a911ca6
Source dataset
uspto-grants-2015_06
Patent number
US09067905B2

Reaction notes

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