Methane → HCID 68139456, compound

HRID 1659139Notes

Reaction equation

HRID 1659139 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 two and a half 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 residual liquid reaches a volume of 50 cc., boiling acetonitrile (200 cc.) is added. After cooling for two 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 twenty-four hours at 2°C., the crystals which have appeared are filtered off, washed three times with ice-cold acetronitrile (total 10 cc.) and dried under reduced presssure (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 two and a half 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 two 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. waitAfter twenty-four hours at 2°C.
  20. filtrationthe crystals which have appeared are filtered off
  21. washwashed three times with ice-cold acetronitrile (total 10 cc.)
  22. customdried under reduced presssure (20 mm. Hg)

Sources & evidence

ORD record
ord-10ca9a31ba584e2290ee15b3632b3f2e
Source dataset
uspto-grants-1976_06
Patent number
US03966931

Reaction notes

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