Tetrahydrofuran → 4-(3-Bromo-benzenesulfinyl)-5-nitro-thiophene-2-carbonitrile

HRID 252225Notes

Reaction equation

HRID 252225 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:10]#[N:11])[S:5][C:6]=1[N+:7]([O-:9])=[O:8].[Br:12][C:13]1[CH:14]=[C:15]([SH:19])[CH:16]=[CH:17][CH:18]=1.C(N(CC)CC)C.C1C[O:30]CC1>>[Br:12][C:13]1[CH:14]=[C:15]([S:19]([C:2]2[CH:3]=[C:4]([C:10]#[N:11])[S:5][C:6]=2[N+:7]([O-:9])=[O:8])=[O:30])[CH:16]=[CH:17][CH:18]=1

Participants

5

Reactant 4

HCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 80597m-BromobenzenethiolHCID 218213104-Bromo-5-nitrothiophene-2-carbonitrile

Product 1

HCID 668532114-(3-Bromo-benzenesulfinyl)-5-nitro-thiophene-2-carbonitrileYield 60%

Procedure

A 12-L, three neck, round bottom flask equipped with a mechanical stirrer and temperature probe was charged with 4-Bromo-5-nitro-thiophene-2-carbonitrile (Example 25: step d; 273 g, 1.174 mol), 3-bromothiophenol (127 mL, 1.232 mol) and THF (4 L). A cold water bath was added. Triethylamine (172 mL, 1.232 mol) was charged to a 250 mL addition funnel and added dropwise to the mixture over 45 min, resulting in a temperature increase from 16.9° C. to 22.3° C. After 1 hour, the reaction was complete and transferred in portions to a 5-L rotary evaporator bulb and concentrated to dryness under vacuum. The solids were transferred to a 110-L glass carboy, diluted with EtOAc (2 L) and satd. NaHCO3 (2 L) and stirred vigorously. The resulting solid precipitate was removed by filtration, washed with H2O (1 L) and dried in a vacuum oven resulting in the title compound as a bright yellow powder (241.56 g, 60%). 1H-NMR (DMSO): δ 8.0 (1H, s), 7.8 (1H, d), 7.6 (1H, d), 7.3 (1H, t), 7.1 (1H, s).

Workup

  1. additionA cold water bath was added
  2. additionadded dropwise to the mixture over 45 min
  3. customresulting in a temperature
  4. temperatureincrease from 16.9° C. to 22.3° C
  5. concentrationconcentrated to dryness under vacuum
  6. additiondiluted with EtOAc (2 L)
  7. customThe resulting solid precipitate was removed by filtration
  8. washwashed with H2O (1 L)
  9. customdried in a vacuum oven

Sources & evidence

ORD record
ord-07ea7cf6f7a148a088d17ba1f56539eb
Source dataset
uspto-grants-2011_01
Patent number
US07868023B2

Reaction notes

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