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Acetic Acid → 4-(4-Chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6,7,8-tetrahydropyrazolo[3,4-e][1,4]thiazepine

HRID 1748801
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1748801
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[S:14][CH2:13][C:12]([CH3:15])=[N:11][C:10]3[N:16]([CH3:25])[N:17]=[C:18]([C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=4)[C:9]2=3)=[C:4]([CH3:26])[CH:3]=1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[S:14][CH2:13][CH:12]([CH3:15])[NH:11][C:10]3[N:16]([CH3:25])[N:17]=[C:18]([C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=4)[C:9]2=3)=[C:4]([CH3:26])[CH:3]=1
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Komponenten

5

Edukt 3

HCID 176Acetic Acid2×HCID 5049666Sodium triacetoxyborohydride2×HCID 867241284-(4-Chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6-dihydropyrazolo[3,4-e][1,4]thiazepine

Produkt 1

HCID 1363484524-(4-Chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6,7,8-tetrahydropyrazolo[3,4-e][1,4]thiazepineAusbeute 84 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 111,2-DichloroethaneLösungsmittel

Versuchsvorschrift

A mixture of 4-(4-chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6-dihydropyrazolo[3,4-e][1,4]thiazepine (0.120 g, 0.31 mmol), acetic acid (0.054 mL, 0.94 mmol) and sodium triacetoxyborohydride (0.080 g, 0.38 mmol) in DCE (10 mL) was stirred at rt for about 16 h. Then more acetic acid (0.054 mL, 0.94 mmol) and sodium triacetoxyborohydride (0.080 g, 0.38 mmol) were added and stirring was continued for another 24 h. The resulting mixture was concentrated in vacuo and partitioned between 5% aqueous sodium bicarbonate (40 mL) and ethyl acetate (40 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (40 mL). The combined organic layers were washed with water (15 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate/hexanes 1:1) to give 4-(4-chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6,7,8-tetrahydropyrazolo[3,4-e][1,4]thiazepine (0.100 g, 0.26 mmol, 84%) as a pale yellow solid as a mixture of two diasereomers (ratio 61:39): LC-MS (Table 1, Method e) Rt=8.51 min and 8.76 min, m/z 385 (M+H)+; Major isomer 1H-NMR (CDCl3, Bruker 400 MHz) δ 1.33 (3H, d, J=6.4 Hz) 2.58 (3H, s) 2.62-2.72 (2H, m) 3.43-3.53 (1H, m) 3.84 (3H, s) 4.06 (1H, br s) 6.59 (1H, s) 6.99 (1H, dd, J=8.3, 2.1 Hz) 7.01-7.09 (1H, m) 7.11 (1H, d, J=8.3 Hz) 7.14 (1H, d, J=2.1 Hz) 7.58 (1H, td, J=7.9, 1.9 Hz) 7.77 (1H, d, J=8.0 Hz) 8.44 (1H, d, J=4.6 Hz); Minor diastereomer: 1H-NMR (CDCl3, Bruker 400 MHz) δ 1.21 (3H, d, J=6.6 Hz) 2.55 (1H, dd, J=15.0, 8.0 Hz) 2.61 (3H, s) 2.95 (1H, dd, J=15.0, 4.3 Hz) 3.36-3.43 (1H, m) 3.86 (3H, s) 4.06 (1H, br s) 6.44 (1H, s) 6.96 (1H, dd, J=8.3, 2.1 Hz) 7.01-7.09 (1H, m) 7.06 (1H, d, J=8.0 Hz) 7.12 (1H, d, J=2.1 Hz) 7.56 (1H, td, J=7.9, 1.9 Hz) 7.76 (1H, d, J=8.0 Hz) 8.40 (1H, d, J=4.6 Hz).

Aufarbeitung

  1. stirringstirring
  2. waitwas continued for another 24 h
  3. concentrationThe resulting mixture was concentrated in vacuo
  4. custompartitioned between 5% aqueous sodium bicarbonate (40 mL) and ethyl acetate (40 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with ethyl acetate (40 mL)
  7. washThe combined organic layers were washed with water (15 mL)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified by column chromatography (SiO2, ethyl acetate/hexanes 1:1)

Quellen und Nachweise

ORD-Eintrag
ord-e001c8f3ca80496c9a3c43cb110d83a6
Quelldatensatz
uspto-grants-2015_10
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09150592B2

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