Ethanol → HCID 68139452, compound

HRID 1604960Notes

Reaction equation

HRID 1604960 reaction equation
[OH:1][CH:2]1[N:6]([C:7]2[N:8]=[N:9][C:10]([O:13][CH3:14])=[CH:11][CH:12]=2)[C:5](=[O:15])[C:4]2[S:16][CH2:17][CH2:18][S:19][C:3]1=2.[H-].[Na+].Cl[C:23]([N:25]1[CH2:30][CH2:29][N:28]([CH3:31])[CH2:27][CH2:26]1)=[O:24].C(O)C>O1CCCC1>[CH3:14][O:13][C:10]1[N:9]=[N:8][C:7]([N:6]2[CH:2]([O:1][C:23]([N:25]3[CH2:30][CH2:29][N:28]([CH3:31])[CH2:27][CH2:26]3)=[O:24])[C:3]3[S:19][CH2:18][CH2:17][S:16][C:4]=3[C:5]2=[O:15])=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 702EthanolHCID 24758Sodium hydrideHCID 30169354-Methyl-1-piperazinecarbonyl chlorideHCID 68140446HCID 68140446, compound

Product 1

HCID 68139452HCID 68139452, compoundYield 60.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
5 °C

Procedure

A solution of 5-hydroxy-6-(6-methoxypyridazin-3-yl)-7-oxo-2,3,6,7-tetrahydro-1,4-dithiino[2,3-c]pyrrole (8.9 g.) in anhydrous tetrahydrofuran (90 cc.) is treated for 30 minutes at about 15°-20° C, with sodium hydride (0.87 g.), and a solution of 1-chlorocarbonyl-4-methylpiperazine (19.5 g.) in anhydrous tetrahydrofuran (120 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 taken up in an ice-cold normal aqueous solution of methanesulphonic acid (150 cc.). The acid solution obtained is rapidly washed twice with diethyl ether (total 100 cc.) and then rendered alkaline by adding 10N sodium hydroxide solution (25 cc.). The oil which separates out is extracted three times with methylene chloride (total 300 cc.). The combined organic extracts are washed twice with distilled water (total 100 cc.), dried over anhydrous magnesium sulphate and evaporated. The crystals obtained (8.7 g.; m.p. 196°-198° C.) are dissolved in boiling ethanol (300 cc.). After filtering the boiling solution and then cooling it for 3 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-(6-Methoxypyridazin-3-yl)-5-(4-methylpiperazin-1-yl)carbonyloxy-7-oxo-2,3,6,7-tetrahydro-1,4-dithiino[2,3-c]pyrrole (7.7 g.), melting at 200° C, is thus obtained.

Workup

  1. customAfter evaporating the solvent under reduced pressure (20 mm.Hg)
  2. customThe acid solution obtained
  3. washis rapidly washed twice with diethyl ether (total 100 cc.)
  4. additionby adding 10N sodium hydroxide solution (25 cc.)
  5. extractionThe oil which separates out is extracted three times with methylene chloride (total 300 cc.)
  6. washThe combined organic extracts are washed twice with distilled water (total 100 cc.)
  7. dry with materialdried over anhydrous magnesium sulphate
  8. customevaporated
  9. customThe crystals obtained (8.7 g.; m.p. 196°-198° C.)
  10. dissolutionare dissolved
  11. filtrationAfter filtering the boiling solution
  12. temperaturecooling it for 3 hours at 2° C
  13. filtrationthe crystals which have appeared are filtered off
  14. washwashed three times with ice-cold ethanol (total 45 cc.)
  15. customdried under reduced pressure (20 mm.Hg.)

Sources & evidence

ORD record
ord-be28fbc639df47fa8466fadfd836c5f3
Source dataset
uspto-grants-1976_04
Patent number
US03948917

Reaction notes

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