Acetic Acid → 1-(5-Fluoro-2-nitrobenzylsulfonyl)naphthalene

HRID 2240001Notes

Reaction equation

HRID 2240001 reaction equation
Cl[CH2:2][S:3]([C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1)(=[O:5])=[O:4].[F:16][C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][CH:18]=1.CC(C)([O-])C.[K+].C(O)(=O)C>C1COCC1>[F:16][C:17]1[CH:18]=[CH:19][C:20]([N+:23]([O-:25])=[O:24])=[C:21]([CH2:2][S:3]([C:6]2[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[CH:9]=[CH:8][CH:7]=2)(=[O:5])=[O:4])[CH:22]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 9590p-FluoronitrobenzeneHCID 117366081-((Chloromethyl)sulfonyl)naphthaleneHCID 23665647Potassium tert-butoxide

Product 1

HCID 593041751-(5-Fluoro-2-nitrobenzylsulfonyl)naphthalene

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a chilled mixture of 1-chloromethanesulfonyl-naphthalene (19.7 g, 81.8 mmol) and 1-fluoro-4-nitrobenzene (8.7 mL, 82 mmol) in dry THF (197 mL) was dropwise added 1.0M potassium t-butoxide in THF (205 mL, 205 mmol). The reaction mixture was stirred at ambient temperature under nitrogen for 1.5 hours. Glacial acetic acid (16 mL, 280 mmol) was then added. After stirring at ambient temperature for 1 hour, 40 minutes, the reaction mixture was concentrated and partitioned in warm ethyl acetate and brine. The organic phase was dried with anhydrous magnesium sulfate, filtered and concentrated. The solid residue was stirred in ether, filtered and dried at 82° C. in vacuo for 1 hour. This yielded 1-(5-fluoro-2-nitro-phenylmethanesulfonyl)-naphthalene as a brown/rust-colored solid (19.9 g, 70.6%): MP: 155-160° C.; Mass Spectrum (−EI, [M−H]−) m/z 344. 1HNMR (300 MHz, DMSO-d6): δ8.50-8.52 (m, 1H), 8.33 (d, 1H, J=8.30 Hz), 8.06-8.14 (m, 2H), 7.97 (dd, 1H, J=7.32 Hz and 1.22 Hz), 7.62-7.74 (m, 3H), 7.44-7.48 (m, 1H), 7.23-7.26 (m, 1H), 5.23 ppm (s, 2H). Elemental Analysis for C17H12FNO4S: Calcd: C, 59.12; H, 3.50; N, 4.06; Found: C, 58.77; H, 3.30; N, 3.92.

Workup

  1. stirringAfter stirring at ambient temperature for 1 hour, 40 minutes
  2. concentrationthe reaction mixture was concentrated
  3. custompartitioned in warm ethyl acetate
  4. dry with materialThe organic phase was dried with anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. stirringThe solid residue was stirred in ether
  8. filtrationfiltered
  9. customdried at 82° C. in vacuo for 1 hour

Sources & evidence

ORD record
ord-52f1c49558c44051bb2bebf6a87395d2
Source dataset
uspto-grants-2010_05
Patent number
US07723329B2

Reaction notes

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