Hydrochloric Acid → HCID 87073696, compound

HRID 1777817Notes

Reaction equation

HRID 1777817 reaction equation
N([O-])=O.[Na+].N[C:6]1[CH:11]=[CH:10][C:9]([CH2:12][C:13]([OH:15])=[O:14])=[CH:8][CH:7]=1.Cl.[O:17]([CH2:21][CH3:22])[C:18]([S-:20])=[S:19].[K+].C(=O)([O-])[O-].[Na+].[Na+]>O>[CH2:21]([O:17][C:18]([S:20][C:6]1[CH:11]=[CH:10][C:9]([CH2:12][C:13]([OH:15])=[O:14])=[CH:8][CH:7]=1)=[S:19])[CH3:22]

Participants

7

Reactant 5

HCID 313Hydrochloric Acid2×HCID 10340Sodium CarbonateHCID 145334-Aminophenylacetic acidHCID 2735045Potassium ethylxanthateHCID 23668193Sodium Nitrite

Product 1

HCID 87073696HCID 87073696, compoundYield 73.1%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Conditions

Temperature
45 °C

Procedure

A solution of sodium nitrite (18.4 g, 0.267 mol) in water (133 mL) was added dropwise to a suspension of 2-(4-aminophenyl)acetic acid (40.3 g, 0.267 mol) in water (133 mL) and conc. HCl (54 mL, 0.65 mol) at 0° C. After addition, the reaction mixture was stirred at the same temperature for 45 min. The solution of the cold diazonium salt was then added dropwise to a mixture of potassium ethyl xanthate (49.3 g, 0.31 mol), water (80 mL) and aqueous sodium carbonate solution (200 mL, 2 M) at rt. After addition, the mixture was allowed to warm to 45° C. and stirred at this temperature until gas evolution ceased (about 3 h to overnight). The mixture was cooled to rt and adjusted to pH=1 with conc. HCl. The aqueous layer was extracted with ethyl acetate (3×300 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford crude 2-(4-((ethoxycarbonothioyl)thio)phenyl)acetic acid (50 g, 73%) as a dark red liquid, which was used for next step directly without further purification. 1H NMR (purified by pre-TLC, CDCl3 300 MHz): δ 7.40 (d, J=7.5 Hz, 2H), 7.28 (d, J=7.8 Hz, 2H), 4.54 (q, J=6.9 Hz, 2H), 3.63 (s, 2H), 1.26 (t, J=6.9 Hz, 3H).

Workup

  1. additionAfter addition
  2. additionAfter addition
  3. stirringstirred at this temperature until gas evolution
  4. custom(about 3 h to overnight)
  5. temperatureThe mixture was cooled to rt
  6. extractionThe aqueous layer was extracted with ethyl acetate (3×300 mL)
  7. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3211ae7f669e4dd9a19875ebf87d7922
Source dataset
uspto-grants-2016_02
Patent number
US09266886B2

Reaction notes

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