Hydrochloric Acid → HCID 66760582, compound

HRID 389564Notes

Reaction equation

HRID 389564 reaction equation
[Br:1][C:2]1[C:3](F)=[C:4]([N+:9]([O-])=O)[CH:5]=[CH:6][C:7]=1[F:8].[S-2:13].[Na+].[Na+].Cl.[N:17]([O-])=O.[Na+].C(=O)([O-])[O-].[K+].[K+]>O.[Fe]>[Br:1][C:2]1[C:3]2[S:13][N:17]=[N:9][C:4]=2[CH:5]=[CH:6][C:7]=1[F:8]

Participants

8

Reactant 5

HCID 313Hydrochloric Acid2×HCID 11430Potassium CarbonateHCID 14804Sodium SulfideHCID 137327452-Bromo-1,3-difluoro-4-nitrobenzeneHCID 23668193Sodium Nitrite

Product 1

HCID 66760582HCID 66760582, compoundYield 13%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 962WaterSolvent

Conditions

Temperature
30 °C

Procedure

A mixture of 3-bromo-2,4-difluoronitrobenzene (1.00 g, 4.20 mmol) and sodium sulfide (655.9 mg, 8.404 mmol) in degassed water (20 mL) was heated to 30° C. overnight in a sealed tube. The solution was neutralized with aqueous 2 N hydrochloric acid at rt. The material was extracted with DCM and water, and the organic layer was purified by column chromatography (1% EtOAc:heptane). The purified residue was dissolved in ethanol (20 mL). Iron powder (1.173 g, 21.01 mmol) and aqueous 12 N hydrochloric acid (0.07 mL, 0.84 mmol) were added, and the mixture was heated to 70° C. for 20 min. The solution was cooled to rt and filtered through Celite. The filtrate was concentrated in vacuo, redissolved in acetic acid (20 mL), and sodium nitrite (579.8 mg, 8.404 mmol) was added at rt. After stirring for 10 min, saturated potassium carbonate was added until bubbling stopped. The material was extracted with DCM and saturated aqueous sodium bicarbonate. The organic layer was purified via column chromatography (1% EtOAc:heptane) to afford 125 mg (13%) of the title compound as a white solid. 1H NMR (400 MHz, CDCl3): δ 7.47 (dd, J=8.8, 8.1 Hz, 1 H), 8.56 (dd, J=9.1, 4.0 Hz, 1 H).

Workup

  1. extractionThe material was extracted with DCM and water
  2. customthe organic layer was purified by column chromatography (1% EtOAc:heptane)
  3. dissolutionThe purified residue was dissolved in ethanol (20 mL)
  4. temperaturethe mixture was heated to 70° C. for 20 min
  5. temperatureThe solution was cooled to rt
  6. filtrationfiltered through Celite
  7. concentrationThe filtrate was concentrated in vacuo
  8. dissolutionredissolved in acetic acid (20 mL)
  9. customuntil bubbling
  10. extractionThe material was extracted with DCM and saturated aqueous sodium bicarbonate
  11. customThe organic layer was purified via column chromatography (1% EtOAc:heptane)

Sources & evidence

ORD record
ord-c565141cb0ed49bfb4bac6b2cf43a3c2
Source dataset
uspto-grants-2013_02
Patent number
US08378104B2

Reaction notes

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