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

HRID 17856

反応式

HRID 17856 の反応式
[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

参加物

6

反応物 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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-4b03fac736a64e2c8cfa6ad9f0c03641
出典データセット
uspto-grants-2010_06
特許番号
US07741317B2

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