1-Chloro-4-fluoro-2-nitrobenzene → 2-Amino-4-fluorobenzene-1-thiol

HRID 407282

Reaction equation

HRID 407282 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N+:9]([O-])=O.O.O.O.O.O.O.O.O.O.[S-2:21].[Na+].[Na+]>O>[NH2:9][C:3]1[CH:4]=[C:5]([F:8])[CH:6]=[CH:7][C:2]=1[SH:21]

Participants

4

Reactant 2

HCID 676591-Chloro-4-fluoro-2-nitrobenzeneHCID 73972Sodium sulfide nonahydrate

Product 1

HCID 111054802-Amino-4-fluorobenzene-1-thiolYield 25%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a solution of 2-chloro-5-fluoronitrobenzene (1.81 g, 10.31 mmol) dissolved in 30 mL of deionized water at room temperature was added sodium sulfide nonahydrate (9.90 g, 41.24 mmol) in a single portion. The resulting solution was heated to reflux and stirred under nitrogen for 32 hours. The resulting light yellow solution was then cooled to room temperature and was washed with 5×50 mL of ethyl acetate. The organic phase was dried over anhydrous magnesium sulfate, filtered, and evaporated to yield a yellow oil. The crude material was purified by flash chromatography eluting with CH2Cl2:MeOH=10:1 to yield 0.36 g (25%) of the title compound. MS (m/z, ES+): 144.0 (M+1, 100%); IR (KBr): 3430, 3340, 1615, 1573, 1482, 1281, 1248, 1172, 1124, 1044, 975, 840, 792 cm−1; 1H NMR (300 MHz, ppm, DMSO-d6) δ: 6.89 (dt, 1H), 6.50 (dd, 1H), 6.21 (dt, 1H), 5.80 (br s, 2H).

Workup

  1. temperatureThe resulting solution was heated
  2. temperatureto reflux
  3. washwas washed with 5×50 mL of ethyl acetate
  4. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customto yield a yellow oil
  8. customThe crude material was purified by flash chromatography
  9. washeluting with CH2Cl2

Sources & evidence

ORD record
ord-022647257f5a424ca792ce8d58f398c5
Source dataset
uspto-grants-2014_06
Patent number
US08754233B2

Linked notes

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