Sodium Carbonate → 1-(2-Bromocyclopenten-1-yl)-4-(methylthio)benzene

HRID 37518

Reaction equation

HRID 37518 reaction equation
Br[C:2]1[CH2:6][CH2:5][CH2:4][C:3]=1[Br:7].[CH3:8][S:9][C:10]1[CH:15]=[CH:14][C:13](B(O)O)=[CH:12][CH:11]=1.C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.C(O)C.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>[Br:7][C:3]1[CH2:4][CH2:5][CH2:6][C:2]=1[C:13]1[CH:14]=[CH:15][C:10]([S:9][CH3:8])=[CH:11][CH:12]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27339594-(Methylthio)phenylboronic acidHCID 44385281,2-Dibromocyclopentene

Product 1

HCID 102650591-(2-Bromocyclopenten-1-yl)-4-(methylthio)benzeneYield 32.6%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

Under nitrogen, 36.4 g (161 mmol) of 1,2-dibromocyclopentene (Aldrich) was reacted with 18.0 g (107 mmol) of 4-methylthiophenylboronic acid (Step 1) in 550 mL of toluene, 365 mL of ethanol, and 235 mL of 2M Na2CO3 in the presence of 6.0 g (5 mol %) of Pd(PPh3)4. The reaction was vigorously stirred at reflux overnight and concentrated in vacuo. The residue was dissolved in ethyl acetate and washed with water, dried (MgSO4), and reconcentrated. Purification by silica gel chromatography (Waters Prep-500) with hexane gave 9.39 g (22%) of 1-(2-bromocyclopenten-1-yl)-4-(methylthio)benzene (38 in Synthetic Scheme X when R5 =SCH3 and R1, R2, R3, R4, R6, and R7 =H) as a solid: mp 52°-54° C.; NMR (CDCl3) d 1.98-2.09 (m, 2H), 2.50 (s, 3H), 2.70-2.78 (m, 2H), 2.80-2.89 (m, 2H), 7.24 (d, J=8 Hz, 2H), 7.55 (d, J=8 Hz, 2H).

Workup

  1. temperatureat reflux overnight
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in ethyl acetate
  4. washwashed with water
  5. dry with materialdried (MgSO4)
  6. customPurification by silica gel chromatography (Waters Prep-500) with hexane

Sources & evidence

ORD record
ord-96aea4226b844c8494d24a985e83b967
Source dataset
uspto-grants-1995_05
Patent number
US05420287

Linked notes

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