2-Aminothiophenol → 3-(2-chloro-phenyl)-3,4-dihydro-2H-1,4-benzothiazine

HRID 17856

Reaktionsgleichung

Reaktionsgleichung von HRID 17856
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH:8]1[NH:13][C:12]2[CH:14]=[CH:15][C:16](C(O)(C(F)(F)F)C(F)(F)F)=[CH:17][C:11]=2[S:10][CH2:9]1.NC1C=CC=CC=1S.BrC1C=CC=CC=1C(=O)CCl.[BH3-]C#N.[Na+]>CN(C=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH:8]1[NH:13][C:12]2[CH:14]=[CH:15][CH:16]=[CH:17][C:11]=2[S:10][CH2:9]1

Komponenten

6

Edukt 4

HCID 87132-AminothiophenolHCID 5003444Sodium cyanoborohydrideHCID 45789634o-Bromo-2-chloro-acetophenoneHCID 866121132-[3-(2-Chloro-phenyl)-3,4-dihydro-2H-1,4-benzothiazin-7-yl]-1,1,1,3,3,3-hexafluoro-propan-2-ol

Produkt 1

HCID 687159823-(2-chloro-phenyl)-3,4-dihydro-2H-1,4-benzothiazine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

2-[3-(2-Chloro-phenyl)-3,4-dihydro-2H-1,4-benzothiazin-7-yl]-1,1,1,3,3,3-hexafluoro-propan-2-ol: To 2-amino-benzenethiol (1.07 mL, 10 mmol) in DMF (10 mL) under an argon atmosphere was added o-bromo-2-chloro-acetophenone (1.5 mL, 9.8 mmol) at 0° C. and the reaction was warmed to rt. After 10 min, NaBH3CN (1.5 g, 71 mmol) was added portion-wise over 5 min and the reaction was stirred for 16 h. The reaction was quenched with 1N HCl, then neutralized to pH 8 with conc. NaHCO3. The product was extracted with ether, washed with water, dried over MgSO4, and concentrated. The resulting residue was purified by flash chromatography to give 3-(2-chloro-phenyl)-3,4-dihydro-2H-1,4-benzothiazine (1.7 g). A mixture of this intermediate (420 mg, 1.6 mmol) and hexafluoroacetone: 1.5 H2O (620 mg, 3.2 mmol) in DCM (1 mL) was heated in a sealed tube in a microwave reactor at 160° C. for 80 min. The resulting mixture was purified by flash chromatography to give 200A (260 mg). LC/MS m/z 427.87 (M+H)+. 1H NMR (400 MHz, CDCl3) δ ppm 3.03-3.15 (m, 2H) 5.26 (m, 1H) 6.58 (d, J=8, 1H) 7.24-7.28 (m, 2H) 7.37-7.43 (m, 2H).

Aufarbeitung

  1. customThe reaction was quenched with 1N HCl
  2. extractionThe product was extracted with ether
  3. washwashed with water
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customThe resulting residue was purified by flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-4b03fac736a64e2c8cfa6ad9f0c03641
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07741317B2

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