Methylhydrazine → 1-(3,7-bis(dimethylamino)-10H-phenothiazin-10-yl)ethanone

HRID 705494Notes

Reaction equation

HRID 705494 reaction equation
C[NH:2]N.C[CH2:5][N:6]([CH:10]([CH3:12])[CH3:11])[CH:7](C)C.O.O.O.[Cl-].[CH3:17][C:18]1[SH+:19][CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1.CNN.[C:30]([O:33]C(=O)C)(=O)[CH3:31].C[CH2:38][N:39]([CH:43](C)C)C(C)C>C(#N)C>[CH3:38][N:39]([CH3:43])[C:25]1[CH:24]=[CH:23][C:17]2[N:2]([C:30](=[O:33])[CH3:31])[C:21]3[C:20]([S:19][C:18]=2[CH:26]=1)=[CH:12][C:10]([N:6]([CH3:5])[CH3:7])=[CH:11][CH:22]=3

Participants

7

Reactant 5

HCID 6061MethylhydrazineHCID 7918Acetic AnhydrideHCID 81531DiisopropylethylamineHCID 86628031methylhydrazine Hunig's baseHCID 866280322-Methylthionin-1-ium;chloride;trihydrate

Product 1

HCID 198258321-(3,7-bis(dimethylamino)-10H-phenothiazin-10-yl)ethanoneYield 64%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
32 °C

Procedure

Synthesis using methylhydrazine/Hunig's base in one pot. To a 5000 cm3 reactor vessel under an atmosphere of nitrogen was added methylthioninium chloride trihydrate (0.54 mol, 200 g) and acetonitrile (1000 cm3). Methylhydrazine (1.07 mol, 49.36 g) was added dropwise at 1.5 mL per minute. The temperature of the mixture increased to 32° C. and was stirred for 20 minutes. The yellow/green suspension had acetic anhydride (5.35 mol, 541 g) added and then Hunig's base (diisopropylethylamine) (1.55 mol, 200 g) was added. The mixture was heated at 90° C. for 2 hours. The cooled mixture was then poured carefully into ice water (2000 cm3) in ten 200 cm3 portions while stirring to give a precipitate. The precipitate was stirred for 45 minutes before it was filtered, washed with water (3×250 cm3). and air dried for 30 minutes. The crude material was crystallised from hot ethanol (2750 cm3) to yield the title compound (112.1 g, 64%) as a light grey solid. Mp 137° C.; vmax(KBr)/cm−1 2910 (CH), 2876 (CH), 2856 (CH), 2799 (CH), 1659 (C═O), 1596 (NO2), 1502 (NO2); δH (250 MHz; CDCl3) 2.16 (3H, s, CH3), 2.93 (12H, s, NCH3), 6.59-6.62 (2H, d, J8.5, ArH), 6.69-6.71 (2H, d, J2.75, ArH), 7.08-7.47 (2H, brd s, ArH); δC (62.9 MHz; CDCl3) 170.3 (C═O), 148.9 (ArC), 127.2 (ArC), 127.1 (ArC), 127.0 (ArC), 110.9 (ArC), 110.7 (ArC), 40.7 (NCH3), 22.9 (CH3); m/z (ES) 284.2 (100%, [M−OAc]+), 328.1 (15%, [M+H]+), 350.1 (41%, [M+Na]+).

Workup

  1. customSynthesis
  2. additionadded
  3. temperatureThe mixture was heated at 90° C. for 2 hours
  4. stirringwhile stirring
  5. customto give a precipitate
  6. stirringThe precipitate was stirred for 45 minutes before it
  7. filtrationwas filtered
  8. washwashed with water (3×250 cm3)
  9. customand air dried for 30 minutes
  10. customThe crude material was crystallised from hot ethanol (2750 cm3)

Sources & evidence

ORD record
ord-2dcd7839b0c2430d8e22d240974032e7
Source dataset
uspto-grants-2015_11
Patent number
US09174954B2

Reaction notes

Loading…