Hydrochloric Acid → 2-Chloro-4-isothiocyanatobenzoic acid

HRID 385178

반응식

HRID 385178 반응식
[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]

참가 물질

11

반응물 7

HCID 313Hydrochloric AcidHCID 807IodineHCID 6348Carbon DisulfideHCID 8471TriethylamineHCID 171544-Amino-2-chlorobenzoic acidHCID 24437Sodium SulfiteHCID 516892Sodium Bicarbonate2회

생성물 1

HCID 227310062-Chloro-4-isothiocyanatobenzoic acid수율 62%

시약·촉매·용매 3

HCID 962Water용매3회HCID 8028Tetrahydrofuran용매2회HCID 8857Ethyl Acetate용매2회

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-b03e4b7becd84cedbfd998405342dfd3
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08367857B2

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