Ethanol → HCID 21527071, compound

HRID 1659134Notes

Reaction equation

HRID 1659134 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N:8]2[CH:12]([OH:13])[C:11]3[S:14][CH2:15][CH2:16][S:17][C:10]=3[C:9]2=[O:18])=[N:6][CH:7]=1.[H-].[Na+].Cl[C:22]([N:24]1[CH2:29][CH2:28][N:27]([CH3:30])[CH2:26][CH2:25]1)=[O:23].C(O)C>O1CCCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N:8]2[CH:9]([O:18][C:22]([N:24]3[CH2:29][CH2:28][N:27]([CH3:30])[CH2:26][CH2:25]3)=[O:23])[C:10]3[S:17][CH2:16][CH2:15][S:14][C:11]=3[C:12]2=[O:13])=[N:6][CH:7]=1

Participants

6

Reactant 4

HCID 702EthanolHCID 24758Sodium hydrideHCID 30169354-Methyl-1-piperazinecarbonyl chlorideHCID 21527081HCID 21527081, compound

Product 1

HCID 21527071HCID 21527071, compoundYield 73.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
5 °C

Procedure

A solution of 6-(5-chloropyrid-2-yl)-5-hydroxy-7-oxo-2,3,6,7-tetrahydro-1,4-dithiino[2,3-c]pyrrole (15.0 g.) in anhydrous tetrahydrofuran (150 cc.) is treated for 15 minutes at about 10°-15°C with sodium hydride (1.44 g.), and a solution of 1-chlorocarbonyl-4methylpiperazine (24.4 g.) in anhydrous tetrahydrofuran (200 cc.) is then added, at 5°C. The reaction mixture is stirred for 4 hours at 5°C. After evaporating the solvent under reduced pressure (20 mm.Hg), the residue is dissolved in diethyl ether (450 cc.). The ether solution is rapidly extracted twice with an ice-cold normal aqueous solution of methanesulphonic acid (total 500 cc.). The combined aqueous extracts are rendered alkaline by adding 10N sodium hydroxide solution (100 cc.). The oil which separates out is extracted with methylene chloride (250 cc.) and then with diethyl ether (300 cc.). The combined organic extracts are washed five times with distilled water (total 250 cc.), dried over anhydrous sodium sulphate, treated with decolourising charcoal (0.1 g.) and evaporated. The crystals obtained (18.0 g.; m.p. 170°C.) are dissolved in boiling ethanol (225 cc.). After filtering the boiling solution and then cooling it for three hours at 2°C., the crystals which have appeared are filtered off, washed three times with ice-cold ethanol (total 45 cc.) and dried under reduced pressure (20 mm.Hg). 6-(5-Chloropyrid-2-yl)-5-(4-methylpiperazin-1-yl)carbonyloxy-7-oxo-2,3,6,7-tetrahydro-1,4-dithiino[2,3-c]pyrrole (15.6 g.), melting at 180°C., is thus obtained.

Workup

  1. customAfter evaporating the solvent under reduced pressure (20 mm.Hg)
  2. dissolutionthe residue is dissolved in diethyl ether (450 cc.)
  3. extractionThe ether solution is rapidly extracted twice with an ice-cold normal aqueous solution of methanesulphonic acid (total 500 cc.)
  4. additionby adding 10N sodium hydroxide solution (100 cc.)
  5. extractionThe oil which separates out is extracted with methylene chloride (250 cc.)
  6. washThe combined organic extracts are washed five times with distilled water (total 250 cc.)
  7. dry with materialdried over anhydrous sodium sulphate
  8. additiontreated with decolourising charcoal (0.1 g.)
  9. customevaporated
  10. customThe crystals obtained (18.0 g.; m.p. 170°C.)
  11. dissolutionare dissolved
  12. filtrationAfter filtering the boiling solution
  13. temperaturecooling it for three hours at 2°C.
  14. filtrationthe crystals which have appeared are filtered off
  15. washwashed three times with ice-cold ethanol (total 45 cc.)
  16. customdried under reduced pressure (20 mm.Hg)

Sources & evidence

ORD record
ord-b19072c4a712410bb9d6e9f224e0fc76
Source dataset
uspto-grants-1976_06
Patent number
US03966931

Reaction notes

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