Sodium Bisulfite → HCID 178422620, Verbindung

HRID 1518157Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1518157
[O:1]1[C:5]2([CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]2)[CH2:4][C:3]([CH:11]=O)=[N:2]1.OS([O-])=O.[Na+].[CH3:18][C:19]1[C:20]([NH2:36])=[C:21]([NH2:35])[CH:22]=[C:23]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=2[C:31]([F:34])([F:33])[F:32])[CH:24]=1>CCO>[CH3:18][C:19]1[C:20]2[NH:36][C:11]([C:3]3[CH2:4][C:5]4([CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]4)[O:1][N:2]=3)=[N:35][C:21]=2[CH:22]=[C:23]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=2[C:31]([F:32])([F:33])[F:34])[CH:24]=1

Komponenten

5

Edukt 3

HCID 23665763Sodium BisulfiteHCID 592800585-Methyl-2'-trifluoromethyl-biphenyl-3,4-diamine2×HCID 592801071-Oxa-2-aza-spiro[4.5]dec-2-ene-3-carbaldehyde3×

Produkt 1

HCID 178422620HCID 178422620, VerbindungAusbeute 41 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

1-Oxa-2-aza-spiro[4.5]dec-2-ene-3-carbaldehyde (135 mg, 0.807 mmol, as prepared in Example 19, step B) was placed in a 4 mL vial equipped with a magnetic stir bar. 40% Aqueous NaHSO3 (0.8 mL) was added via syringe, and the mixture stirred at rt for 2 h. 5-Methyl-2′-trifluoromethyl-biphenyl-3,4-diamine (246 mg, 0.923 mmol, as prepared in the previous step) was placed in an 8 mL vial equipped with a magnetic stir bar. EtOH (2 mL) was added. The 1-oxa-2-aza-spiro[4.5]dec-2-ene-3-carbaldehyde solution was added to the 5-methyl-2′-trifluoromethyl-biphenyl-3,4-diamine solution. The flask which had contained the 1-oxa-2-aza-spiro[4.5]dec-2-ene-3-carbaldehyde solution was rinsed with EtOH (0.5 mL) and water (0.25 mL), and this was also added to the 5-methyl-2′-trifluoromethyl-biphenyl-3,4-diamine solution. The mixture was heated to 90° C. for 2 h. The mixture was poured into water, and the precipitate was isolated by filtration. The solid was washed with water, dissolved in EtOAc, dried over MgSO4, filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography using a 40-g SiO2 pre-packed column eluting with EtOAc/heptane, 0:1 to 3:7, v/v over 30 min, yielding 136 mg (41%) of the title compound. 1H-NMR (400 MHz, d4-MeOH) δ: 7.76 (d, J=7.8 Hz, 1H), 7.61 (t, J=7.5 Hz, 1H), 7.52 (t, J=7.6 Hz, 1H), 7.26-7.49 (m, 2H), 7.03 (br. s., 1H), 2.63 (br. s., 3H), 1.69-1.88 (m, 6H), 1.45-1.63 (m, 4H).

Aufarbeitung

  1. customvial equipped with a magnetic stir bar
  2. customvial equipped with a magnetic stir bar
  3. washwas rinsed with EtOH (0.5 mL) and water (0.25 mL)
  4. additionthis was also added to the 5-methyl-2′-trifluoromethyl-biphenyl-3,4-diamine solution
  5. temperatureThe mixture was heated to 90° C. for 2 h
  6. additionThe mixture was poured into water
  7. customthe precipitate was isolated by filtration
  8. washThe solid was washed with water
  9. dissolutiondissolved in EtOAc
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. customthe solvent was removed under reduced pressure
  13. customThe residue was purified by column chromatography
  14. washeluting with EtOAc/heptane, 0:1 to 3:7, v/v over 30 min

Quellen und Nachweise

ORD-Eintrag
ord-888816eb401542bb9ced50fd0d04f069
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08232409B2

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