Methane → HCID 68139456, compound

HRID 1604964Notes

Reaction equation

HRID 1604964 reaction equation
[OH:1][CH:2]1[N:6]([C:7]2[CH:16]=[CH:15][C:14]3[C:9](=[N:10][CH:11]=[CH:12][CH:13]=3)[N:8]=2)[C:5](=[O:17])[C:4]2[S:18][CH2:19][CH2:20][S:21][C:3]1=2.[H-].[Na+].Cl[C:25]([N:27]1[CH2:32][CH2:31][N:30]([CH3:33])[CH2:29][CH2:28]1)=[O:26].C>CN(C)C=O.C(#N)C>[CH3:33][N:30]1[CH2:31][CH2:32][N:27]([C:25]([O:17][CH:5]2[N:6]([C:7]3[CH:16]=[CH:15][C:14]4[C:9](=[N:10][CH:11]=[CH:12][CH:13]=4)[N:8]=3)[C:2](=[O:1])[C:3]3[S:21][CH2:20][CH2:19][S:18][C:4]2=3)=[O:26])[CH2:28][CH2:29]1

Participants

7

Reactant 4

HCID 297MethaneHCID 24758Sodium hydrideHCID 30169354-Methyl-1-piperazinecarbonyl chlorideHCID 68139283HCID 68139283, compound

Product 1

HCID 68139456HCID 68139456, compoundYield 49.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

5-Hydroxy-6-(1,8-naphthyridin-2-yl)-7-oxo-2,3,6,7-tetrahydro-1,4-dithiino[2,3-c]pyrrole (8.45 g.) is added, at 0° C, to a suspension of sodium hydride (0.8 g.) in anhydrous dimethylformamide (125 cc.). The reaction mixture is stirred for half an hour at 0° C, and 1-chlorocarbonyl-4-methylpiperazine (8.45 g.) dissolved in anhydrous dimethylformamide (50 cc.) is then added. After stirring for 21/2 hours at 5° C., the reaction mixture is diluted with ice-water (500 cc.). The precipitate which has appeared is filtered off, washed four times with distilled water (total 200 cc.) and twice with diethyl ether (total 50 cc.) and then dissolved in methylene chloride (300 cc.). The organic solution is washed four times with distilled water (total 160 cc.), dried over anhydrous sodium sulphate, treated with decolourising charcoal (0.2 g.) and evaporated. When the residue liquid reaches a volume of 50 cc., boiling acetonitrile (200 cc.) is added. After cooling for 2 hours at 2° C., the crystals which have appeared are filtered off, washed three times with ice-cold acetonitrile (total 15 cc.) and dried under reduced pressure (20 mm. Hg). The crystals thus isolated (8.0 g.) are dissolved in boiling acetonitrile (270 cc.), decolourising charcoal (0.2 g.) is added to the boiling solution and the whole is filtered. After 24 hours at 2° C., the crystals which have appeared are filtered off, washed three times with ice-cold acetonitrile (total 10 cc.) and dried under reduced pressure (20 mm. Hg). 5-(4-Methylpiperazin-1-yl)carbonyloxy-6-(1,8-naphthyridin-2-yl)-7-oxo-2,3,6,7-tetrahydro-1,4-dithiino[2,3-c]pyrrole (5.8 g.), melting at 255° C., is thus obtained.

Workup

  1. additionis then added
  2. stirringAfter stirring for 21/2 hours at 5° C.
  3. filtrationThe precipitate which has appeared is filtered off
  4. washwashed four times with distilled water (total 200 cc.)
  5. dissolutiontwice with diethyl ether (total 50 cc.) and then dissolved in methylene chloride (300 cc.)
  6. washThe organic solution is washed four times with distilled water (total 160 cc.)
  7. dry with materialdried over anhydrous sodium sulphate
  8. additiontreated with decolourising charcoal (0.2 g.)
  9. customevaporated
  10. additionis added
  11. temperatureAfter cooling for 2 hours at 2° C.
  12. filtrationthe crystals which have appeared are filtered off
  13. washwashed three times with ice-cold acetonitrile (total 15 cc.)
  14. customdried under reduced pressure (20 mm. Hg)
  15. customThe crystals thus isolated (8.0 g.)
  16. dissolutionare dissolved
  17. additionis added to the boiling solution
  18. filtrationthe whole is filtered
  19. filtrationthe crystals which have appeared are filtered off
  20. washwashed three times with ice-cold acetonitrile (total 10 cc.)
  21. customdried under reduced pressure (20 mm. Hg)

Sources & evidence

ORD record
ord-2ce3dfaf4f7246ac978d65db9ba9b090
Source dataset
uspto-grants-1976_04
Patent number
US03948917

Reaction notes

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