Hydrochloric Acid → 2-Chloro-4-isothiocyanatobenzoic acid

HRID 385178

反応式

HRID 385178 の反応式
[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]

参加物

11

反応物 7

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

生成物 1

HCID 227310062-Chloro-4-isothiocyanatobenzoic acid収率 62%

試薬・触媒・溶媒 3

HCID 962Water溶媒3 回HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒2 回

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-b03e4b7becd84cedbfd998405342dfd3
出典データセット
uspto-grants-2013_02
特許番号
US08367857B2

関連ノート

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