Sulfuric Acid → HCID 54370116, compound

HRID 1183632Notes

Reaction equation

HRID 1183632 reaction equation
F[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[F:12][C:13]([F:17])([F:16])[CH2:14][OH:15].[OH-].[Na+].OS(O)(=O)=O>C1(C)C=CC=CC=1.O>[F:8][C:6]1[CH:5]=[CH:4][C:3]([N+:9]([O-:11])=[O:10])=[C:2]([O:15][CH2:14][C:13]([F:17])([F:16])[F:12])[CH:7]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 64092,2,2-TrifluoroethanolHCID 14798Sodium HydroxideHCID 679672,4-Difluoronitrobenzene

Product 1

HCID 54370116HCID 54370116, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
47.5 °C

Procedure

To a solution of 2,4-difluoronitrobenzene (300.0 g, 1.89 mol) and 2,2,2-trifluoroethanol (245.0 g, 2.45 mol) in toluene (600 mL) was added sodium hydroxide (90.5 g, 2.26 mol) in portions over 30 min to keep the temperature between 30 and 40° C. After the temperature had dropped to 30° C., the reaction mixture was heated to 45-50° C. using an oil bath for additional 16 h. After cooling, water (500 mL) and 2.5 N H2SO4 (200-300 mL, for adjustment of pH to 5) were added and the organic layer was separated. The water layer was extracted with EtOAc (2×300 mL). The combined organic layers were washed with saturated sodium chloride solution (100 mL) and dried over magnesium sulfate. The solvent was evaporated to give a yellow oil, which solidified after 30 min to give a yellowish solid (450.0 g, quantitative). The crude product was used in the next step without purification. 1H NMR (300 MHz, CDCl3/TMS): δ 8.03-7.98 (m, 1H), 6.93-6.82 (m, 2H), 4.49 (q, J=7.7 Hz, 2H). 13C NMR (75 MHz, CDCl3/TMS): δ 165.0 (d, 1JCF=259.6 Hz), 152.3 (d, 3JCF=13.1 Hz), 128.2 (d, 3JCF=11.9 Hz), 122.4 (d, 1JCF=273.4 Hz), 110.1 (d, 2JCF=22.5 Hz), 105.9 (q, 1JCF=242.6 Hz), 104.3 (d, 2JCF=26.1 Hz), 67.6 (q, 1JCF=36.7 Hz).

Workup

  1. customthe temperature between 30 and 40° C
  2. additionAfter the temperature had dropped to 30° C.
  3. customfor additional 16 h
  4. temperatureAfter cooling
  5. customthe organic layer was separated
  6. extractionThe water layer was extracted with EtOAc (2×300 mL)
  7. washThe combined organic layers were washed with saturated sodium chloride solution (100 mL)
  8. dry with materialdried over magnesium sulfate
  9. customThe solvent was evaporated
  10. customto give a yellow oil, which
  11. customto give a yellowish solid (450.0 g, quantitative)
  12. customThe crude product was used in the next step without purification

Sources & evidence

ORD record
ord-7579c40dcc7545b3a4efedcb36042d23
Source dataset
uspto-grants-2014_03
Patent number
US08664249B2

Reaction notes

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