Hydrogen Sulfide → HCID 15925305, compound

HRID 704207Notes

Reaction equation

HRID 704207 reaction equation
[CH3:1][N:2]([CH3:23])[CH2:3][CH:4]([N:6]1[C:19]2[CH:18]=[C:17]([C:20](=[S:22])[NH2:21])[CH:16]=[CH:15][C:14]=2[S:13][C:12]2[C:7]1=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH3:5].[CH:24]1([CH2:30]N)[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]1.S>C(O)C>[CH:24]1([CH2:30][NH:21][C:20]([C:17]2[CH:16]=[CH:15][C:14]3[S:13][C:12]4[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=4)[N:6]([CH:4]([CH3:5])[CH2:3][N:2]([CH3:1])[CH3:23])[C:19]=3[CH:18]=2)=[S:22])[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]1

Participants

5

Reactant 3

HCID 402Hydrogen SulfideHCID 76688CyclohexanemethylamineHCID 15925238HCID 15925238, compound

Product 1

HCID 15925305HCID 15925305, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
125 °C

Procedure

A mixture of 10-[(2RS)-1-dimethylamino-2-propyl]-2-phenothiazinecarbothioamide (2 g) and cyclohexylmethylamine 11.4 cc) in absolute ethanol (30 cc) is saturated with hydrogen sulphide and heated for 16 hours to a temperature in the region of 125° C. After cooling, the orange solution obtained is concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C. The residual orange oil is purified by chromatography on a column (height: 25 cm; diameter: 4 cm) of silica gel (0.06-0.04 mm) under a slight excess pressure of nitrogen (40 kPa) eluting with a 60:40 by volume mixture (1 litre) of ethyl acetate and cyclohexane and collecting 60-cc fractions. The combined fractions 6 to 13 are concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C. The residual orange gum (2.5 g) is dissolved in isopropanol (8 cc) under reflux and treated, with stirring, with a solution at 50° C. of fumaric acid (0.6 g) in isopropanol (8 cc). The mixture is allowed to cool and stirring is continued for 1 hour at a temperature in the region of 5° C. The solid formed is drained, washed with isopropanol (2×1 cc) and dried under reduced pressure (5 mm Hg; 0.68 kPa) at 40° C. N-Cyclohexylmethyl-10-[(2RS)-1-dimethylamino-2-propyl]-2-phenothiazinecarbothioamide neutral fumarate (2.53 g) is thereby obtained in the form of a yellow solid, m.p. 167° C.

Workup

  1. temperatureAfter cooling
  2. customthe orange solution obtained
  3. concentrationis concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C
  4. customThe residual orange oil is purified by chromatography on a column (height: 25 cm; diameter: 4 cm) of silica gel (0.06-0.04 mm) under a slight excess pressure of nitrogen (40 kPa)
  5. washeluting with a 60:40 by volume mixture (1 litre) of ethyl acetate and cyclohexane
  6. customcollecting 60-cc fractions
  7. concentrationThe combined fractions 6 to 13 are concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C
  8. dissolutionThe residual orange gum (2.5 g) is dissolved in isopropanol (8 cc)
  9. temperatureunder reflux
  10. additiontreated
  11. temperatureto cool
  12. stirringstirring
  13. customThe solid formed
  14. washwashed with isopropanol (2×1 cc)
  15. customdried under reduced pressure (5 mm Hg; 0.68 kPa) at 40° C

Sources & evidence

ORD record
ord-bf843516aedc42e3ae9040fe5bcbca4d
Source dataset
uspto-grants-1991_01
Patent number
US04985419

Reaction notes

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