Hydrochloric Acid → 2-Chloro-4-isothiocyanatobenzoic acid

HRID 385178

Reaktionsgleichung

Reaktionsgleichung von HRID 385178
[C:1](=[S:3])=S.[NH2:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[C:7]([Cl:14])[CH:6]=1.C(N(CC)CC)C.II.Cl.S([O-])([O-])=O.[Na+].[Na+].C(=O)([O-])O.[Na+]>O.C(OCC)(=O)C.O1CCCC1>[N:4]([C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[C:7]([Cl:14])[CH:6]=1)=[C:1]=[S:3]

Komponenten

11

Edukt 7

HCID 313Hydrochloric AcidHCID 807IodineHCID 6348Carbon DisulfideHCID 8471TriethylamineHCID 171544-Amino-2-chlorobenzoic acidHCID 24437Sodium SulfiteHCID 516892Sodium Bicarbonate2×

Produkt 1

HCID 227310062-Chloro-4-isothiocyanatobenzoic acidAusbeute 62 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittel3×HCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel2×

Versuchsvorschrift

Carbon disulfide (0.26 mL, 4.4 mmol) was added to a mixture comprising 4-amino-2-chlorobenzoic acid (0.26 g, 1.5 mmol), tetrahydrofuran (1.0 mL), water (1.0 mL) and triethylamine (0.51 mL, 3.6 mmol), followed by stirring at room temperature for 24.5 hours. To the obtained reaction mixture, a tetrahydrofuran (1.0 mL) solution of iodine (0.41 g, 1.6 mmol) was dropwise added over a period of 5 minutes at 0° C., followed by stirring at 0° C. for further two hours. Thereafter, 1M hydrochloric acid (1.5 mL) and sodium sulfite (38 mg, 0.30 mmol) were added and stirred. Then, ethyl acetate (6 mL) was added, and the organic layer was separated and concentrated under reduced pressure to dryness. To the residue, water (4 mL) and sodium hydrogencarbonate (0.14 g, 1.7 mmol) were added, and the insoluble matter was removed by filtration. To the filtrate, 1M hydrochloric acid (1.5 mL) and water (2.0 mL) were added, and the precipitated solid was collected by filtration. To this solid, ethyl acetate (6 mL), water (2.0 mL) and sodium hydrogencarbonate (25 mg, 1.7 mmol) were added, and the organic layer was concentrated under reduced pressure to dryness to obtain 4-isothiocyanato-2-chlorobenzoic acid as a white solid (0.20 g, yield: 62%, HPLC purity: 91%, HPLC retention time: 3.9 min). LC-MS ES-212, 214 (retention time: 4.2 min, condition 1).

Aufarbeitung

  1. customTo the obtained reaction mixture
  2. stirringby stirring at 0° C. for further two hours
  3. stirringstirred
  4. customthe organic layer was separated
  5. concentrationconcentrated under reduced pressure to dryness
  6. customthe insoluble matter was removed by filtration
  7. additionTo the filtrate, 1M hydrochloric acid (1.5 mL) and water (2.0 mL) were added
  8. filtrationthe precipitated solid was collected by filtration
  9. concentrationthe organic layer was concentrated under reduced pressure to dryness

Quellen und Nachweise

ORD-Eintrag
ord-b03e4b7becd84cedbfd998405342dfd3
Quelldatensatz
uspto-grants-2013_02
Patentnummer
US08367857B2

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