Tetrahydrofuran → Methyl 4-bromo-3-((methylthio)methyl)benzoate

HRID 219834Notes

Reaction equation

HRID 219834 reaction equation
[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH2:12]Br.COCC1C=C(C(O)=O)C=CC=1C1C=CC=CC=1C.C1COCC1.[CH3:38][S-:39].[Na+]>CC#N>[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH2:12][S:39][CH3:38]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 4378561Sodium methanethiolateHCID 11460987Methyl 4-Bromo-3-(bromomethyl)benzoateHCID 594958222-(Methoxymethyl)-2'-methylbiphenyl-4-carboxylic acid

Product 1

HCID 67529193Methyl 4-bromo-3-((methylthio)methyl)benzoateYield 94%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of methyl 4-bromo-3-(bromomethyl)benzoate, which preparation is described above, under Intermediate 28, Step 1, (2 g; 6.49 mmol; 1 eq.) in CH3CN (10 mL) and THF (10 mL) was added sodium thiomethoxide (0.50 g; 7.14 mmol; 1.10 eq.) and the mixture was stirred at reflux for 1 hour and at RT overnight. After concentration under vacuum, the mixture was partitioned between EtOAc and water. The organic layer was washed with NaCl sat. solution, dried over magnesium sulfate, filtered off and dried under vacuum to give the title compound as a yellow oil (1.7 g, 94%). 1H NMR (CDCl3) δ 7.99 (d, J=2.3 Hz, 1H), 7.77 (dd, J=8.3, 2.1 Hz, 1H), 7.65 (d, J=8.3 Hz, 1H), 3.92 (s, 3H), 3.83 (s, 2H), 2.06 (s, 3H). HPLC (Method A) Rt 4.31 min (Purity: 87.4%).

Workup

  1. concentrationAfter concentration under vacuum
  2. customthe mixture was partitioned between EtOAc and water
  3. washThe organic layer was washed with NaCl sat. solution
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered off
  6. customdried under vacuum

Sources & evidence

ORD record
ord-53054996cc744b05937156afcca79d47
Source dataset
uspto-grants-2012_06
Patent number
US08202865B2

Reaction notes

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