1,2-Ethanedithiol → HCID 14502136, compound

HRID 1165786Notes

Reaction equation

HRID 1165786 reaction equation
C(S)CS.[BH4-].[Na+].[C:7]([C:9]1[CH:22]=[CH:21][C:20]2[S:19][C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[N:12]([CH:23]([CH3:29])[C:24](OCC)=[O:25])[C:11]=2[CH:10]=1)#[N:8].[OH-].[Na+]>O1CCCC1.C(Cl)Cl>[OH:25][CH2:24][CH:23]([N:12]1[C:11]2[CH:10]=[C:9]([C:7]#[N:8])[CH:22]=[CH:21][C:20]=2[S:19][C:18]2[C:13]1=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH3:29]

Participants

7

Reactant 4

HCID 109021,2-EthanedithiolHCID 14798Sodium Hydroxide2×HCID 4311764Sodium borohydrideHCID 14502135ethyl (2RS)-2-(2-cyano-10-phenothiazinyl)propionate

Product 1

HCID 14502136HCID 14502136, compoundYield 65.9%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
20 °C

Procedure

1,2-ethanedithiol (113 cc) is poured into a suspension of sodium borohydride (52 g) in tetrahydrofuran (1.4 liters), with stirring, in 15 minutes and at a temperature of about 20° C., and then a solution of ethyl (2RS)-2-(2-cyano-10-phenothiazinyl)propionate (296 g) in tetrahydrofuran (1.4 liters) is poured in 15 minutes under the same conditions. At the end of the addition, the reaction mixture is heated for 20 hours at a temperature of about 60° C. After cooling to a temperature of 5° C., a 4N aqueous solution of sodium hydroxide (1 liter) is poured in over 1 hour: a strong evolution of gas is observed. The reaction mixture is then poured into a mixture of a 4N aqueous solution of sodium hydroxide (1 liter) and methylene chloride (3 liters), while stirring. The organic phase is isolated and the aqueous phase is again extracted with methylene chloride (1 liter). The pooled organic phases are washed with a saturated aqueous solution of sodium chloride (2×1 liter), dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C. The viscous orange oil (290 g) is purified on a column (height: 50 cm; diameter: 8.5 cm) of silica gel (0.2-0.063 mm), eluting successively with methylene chloride (3 liters), then a mixture of methylene chloride and methanol (97.5-2.5 by volume) (4 liters) and with a mixture of methylene chloride and methanol (95-5 by volume) (10 liters) and collecting fractions of 1 liter. Fractions 3 to 15 are pooled and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C. 10-[(2RS)1-hydroxy-2-propyl]- 2-phenothiazinecarbonitrile (169.7 g) is thus obtained in the form of a yellow solid which melts at 123° C.

Workup

  1. additionAt the end of the addition
  2. temperaturethe reaction mixture is heated for 20 hours at a temperature of about 60° C
  3. temperatureAfter cooling to a temperature of 5° C.
  4. stirringwhile stirring
  5. customThe organic phase is isolated
  6. extractionthe aqueous phase is again extracted with methylene chloride (1 liter)
  7. washThe pooled organic phases are washed with a saturated aqueous solution of sodium chloride (2×1 liter)
  8. dry with materialdried over magnesium sulphate
  9. filtrationfiltered
  10. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C
  11. customThe viscous orange oil (290 g) is purified on a column (height: 50 cm; diameter: 8.5 cm) of silica gel (0.2-0.063 mm)
  12. washeluting successively with methylene chloride (3 liters)
  13. additiona mixture of methylene chloride and methanol (97.5-2.5 by volume) (4 liters)
  14. additionwith a mixture of methylene chloride and methanol (95-5 by volume) (10 liters)
  15. customcollecting fractions of 1 liter
  16. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C

Sources & evidence

ORD record
ord-7fc0fd87851f43778e13c7d4624164cb
Source dataset
uspto-grants-1990_03
Patent number
US04912105

Reaction notes

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