تفاعل #44411

معادلة التفاعل

N,N-Diethyl-m-ethyl-p-phenylenediamine dihydrochloride

sodium sulphide

sodium chloride

→

title compound

المردود 6.2%

1,9-Diethyl Ethylthioninium chloride

المردود 6.2%

المذيبات

water

ظروف التفاعل

المعالجة

1. 1
   workup.ADDITIONadded portion-wise
2. 2
   workup.ADDITIONwas added
3. 3
   ترشيحbefore filtering
4. 4
   غسيلwashing the precipitate with water
5. 5
   غسيلThe precipitate was also washed with ethanol
6. 6
   تركيزthe ethanol concentrated
7. 7
   أخرىto give a sticky purple solid
8. 8
   ترشيحThe suspension was filtered
9. 9
   workup.DISSOLUTIONthe solid dissolved in dichloromethane (100 cm3)
10. 10
    تجفيفmethanol (10 cm3) before drying over magnesium sulphate
11. 11
    ترشيحFiltering
12. 12
    تركيزconcentration with the ethanol soluble product

الإجراء التجريبي

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?.

المصدر