Sodium Chloride → 1,9-Diethyl ethylthioninium chloride

HRID 2382617Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2382617
[ClH:1].Cl.C(N(CC)[C:6]1[CH:11]=[CH:10][C:9](N)=[C:8]([CH2:13][CH3:14])[CH:7]=1)C.[S-2:17].[Na+].[Na+].[Cl-].[Na+]>O.[Fe](Cl)(Cl)Cl>[Cl-:1].[CH2:13]([CH:8]([C:9]1[SH+:17][C:11]([CH2:10][CH3:9])=[CH:6][CH:7]=[CH:8][CH:6]=[CH:11][CH:10]=1)[CH3:7])[CH3:14]

Komponenten

6

Edukt 3

HCID 5234Sodium ChlorideHCID 14804Sodium SulfideHCID 68622659n,n-Diethyl-m-ethyl-p-phenylenediamine dihydrochloride

Produkt 1

HCID 1317281781,9-Diethyl ethylthioninium chlorideAusbeute 6,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24380Iron chloride (FeCl3)Katalysator2×HCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
5 °C

Versuchsvorschrift

N,N-Diethyl-m-ethyl-p-phenylenediamine dihydrochloride (2 g, 7.5 mmol) was dissolved in water (75 cm3) and the solution adjusted to pH 1.6. The pink solution then had sodium sulphide (>60%) (1.35 g, 10.4 mmol) added portion-wise. To the suspension was added an aqueous solution of iron (III) chloride (4.22 g, 15.6 mmol in 35 cm3 of water) where there was an immediate colour change to purple. The solution was then aerated for 1 hour before a second portion of iron (III) chloride (4.22 g, 15.6 mmol in 35 cm3 of water) solution was added. The solution was cooled to 5° C. before filtering and washing the precipitate with water. The precipitate was also washed with ethanol and the ethanol concentrated to give a sticky purple solid. To the aqueous filtrate was added sodium chloride (50 g) and the solution was stirred for 10 minutes whereby the colour changed to red/purple as the product was salted out. The suspension was filtered and the solid dissolved in dichloromethane (100 cm3) and methanol (10 cm3) before drying over magnesium sulphate. Filtering and concentration with the ethanol soluble product gave the title compound (0.06 g, 3%) as a purple solid. δH (250 MHz; D2O): 6.73 (2H, s, ArH), 6.48 (2H, s, ArH), 3.45 (8H, brdq, NCH2), 2.46 (4H, q, 7.5, CH2), 1.17 (12H, brdt, CH3), 0.93 (6H, t, 7.5, CH3); m/z (ESI) 396.2 (100%, [M-Cl]+). Optionally, flash column chromatography was performed to remove iron-chloride residues, with 10% methanol: 90% dichloromethane as eluent and using silica 40-63μ 60 Å.

Aufarbeitung

  1. additionadded portion-wise
  2. additionwas added
  3. filtrationbefore filtering
  4. washwashing the precipitate with water
  5. washThe precipitate was also washed with ethanol
  6. concentrationthe ethanol concentrated
  7. customto give a sticky purple solid
  8. filtrationThe suspension was filtered
  9. dissolutionthe solid dissolved in dichloromethane (100 cm3)
  10. dry with materialmethanol (10 cm3) before drying over magnesium sulphate
  11. filtrationFiltering
  12. concentrationconcentration with the ethanol soluble product

Quellen und Nachweise

ORD-Eintrag
ord-2c3b425fc96249e68d5e29d18c6c0dcc
Quelldatensatz
uspto-grants-2012_09
Patentnummer
US08263589B2

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