Sodium Chloride → 1,9-Diethyl ethylthioninium chloride

HRID 16133

反応式

HRID 16133 の反応式
[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]

参加物

6

反応物 3

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

生成物 1

HCID 1317281781,9-Diethyl ethylthioninium chloride収率 6.2%

試薬・触媒・溶媒 2

HCID 24380Iron chloride (FeCl3)触媒2 回HCID 962Water溶媒

反応条件

温度
5 °C

実験手順

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. dH (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?.

後処理

  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

出典と根拠

ORDレコード
ord-f6bc02b24f0e498097482588d1a6235a
出典データセット
uspto-grants-2010_06
特許番号
US07737138B2

関連ノート

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