Hydrogen Sulfide → HCID 15925252, compound

HRID 704171Notes

Reaction equation

HRID 704171 reaction equation
[CH3:1][N:2]([CH2:6][CH:7]([N:9]1[C:22]2[CH:21]=[C:20]([C:23]#[N:24])[CH:19]=[CH:18][C:17]=2[S:16][C:15]2[C:10]1=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH3:8])[CH2:3][CH2:4][CH3:5].C(N(CC)CC)C.[SH2:32]>N1C=CC=CC=1.C(OCC)(=O)C>[CH3:1][N:2]([CH2:6][CH:7]([N:9]1[C:22]2[CH:21]=[C:20]([C:23](=[S:32])[NH2:24])[CH:19]=[CH:18][C:17]=2[S:16][C:15]2[C:10]1=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH3:8])[CH2:3][CH2:4][CH3:5]

Participants

6

Reactant 3

HCID 402Hydrogen SulfideHCID 8471TriethylamineHCID 15925255HCID 15925255, compound

Product 1

HCID 15925252HCID 15925252, compound

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

A solution of 10-[(2RS)-1-(N-methyl-N-propylamino)-2-propyl]-2-phenothiazinecarbonitrile (4.3 g) and triethylamine (1.77 cc) in pyridine (86 cc) is treated with hydrogen sulphide and left stirred for 16 hours at a temperature in the region of 20° C. The green solution obtained is diluted with ethyl acetate (200 cc), washed with distilled water (5×40 cc), dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C. The residual oil (5.4 g) is purified by chromatography on a column (height: 30 cm; diameter: 5.5 cm) of silica gel (0.04-0.063 mm) with a slight excess pressure of nitrogen (40 kPa), eluting with a mixture (97.5:2.5 by volume) (5 liters) of methylene chloride and methanol and collecting 100-cc fractions. The combined fractions 13 to 44 are concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C. The residual yellow oil (4.37 g) is dissolved in ethanol (12 cc) under reflux and treated, with stirring, with a solution of fumaric acid (1.4 g) in ethanol (15 cc) under reflux. After 2 hours, stirring at a temperature in the region of 5° C., the solid formed is drained, washed with ethanol (5 cc) and dried under reduced pressure (5 mm Hg; 0.68 kPa) at 40° C. 10-[(2RS)-1-(N-Methyl-N-propylamino)-2-propyl]-2-phenothiazinecarbothioamide acid fumarate (4.35 g) is thereby obtained in the form of yellow crystals, m.p. 204° C.

Workup

  1. waitleft
  2. customThe green solution obtained
  3. washwashed with distilled water (5×40 cc)
  4. dry with materialdried over magnesium sulphate
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C
  7. customThe residual oil (5.4 g) is purified by chromatography on a column (height: 30 cm; diameter: 5.5 cm) of silica gel (0.04-0.063 mm) with a slight excess pressure of nitrogen (40 kPa)
  8. washeluting with a mixture (97.5:2.5 by volume) (5 liters) of methylene chloride and methanol
  9. customcollecting 100-cc fractions
  10. concentrationThe combined fractions 13 to 44 are concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C
  11. dissolutionThe residual yellow oil (4.37 g) is dissolved in ethanol (12 cc)
  12. temperatureunder reflux
  13. additiontreated
  14. stirringwith stirring, with a solution of fumaric acid (1.4 g) in ethanol (15 cc)
  15. temperatureunder reflux
  16. waitAfter 2 hours
  17. stirringstirring at a temperature in the region of 5° C.
  18. customthe solid formed
  19. washwashed with ethanol (5 cc)
  20. customdried under reduced pressure (5 mm Hg; 0.68 kPa) at 40° C

Sources & evidence

ORD record
ord-ae4e4e0e6b234ca9bcba005887794d3e
Source dataset
uspto-grants-1991_01
Patent number
US04985419

Reaction notes

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