Carbon Dioxide → 4,5-Dihydro-8-phenyl-5-thioxo-3H,6H-1,4,5a,8a-tetraazaacenaphthylen-3-one

HRID 2073189Notes

Reaction equation

HRID 2073189 reaction equation
[C:1]1([C:7]2[N:12]3[N:13]=[CH:14][C:15]([C:16]([NH2:18])=[O:17])=[C:11]3[NH:10][CH2:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(=O)=O.[H-].[Na+].[C:24](N1C=CN=C1)(N1C=CN=C1)=[S:25]>O1CCCC1.CC(C)=O>[C:1]1([C:7]2[N:12]3[C:11]4[N:10]([C:24](=[S:25])[NH:18][C:16](=[O:17])[C:15]=4[CH:14]=[N:13]3)[CH2:9][CH:8]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 24758Sodium hydrideHCID 802641,1'-ThiocarbonyldiimidazoleHCID 1358568134,5-Dihydro-7-phenylpyrazolo[1,5-a]pyrimidine-3-carboxamide

Product 1

HCID 150440804,5-Dihydro-8-phenyl-5-thioxo-3H,6H-1,4,5a,8a-tetraazaacenaphthylen-3-oneYield 41.7%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 7.6 g of 4,5-dihydro-7-phenylpyrazolo[1,5-a]pyrimidine-3-carboxamide (prepared as described in Example 3) in 304 ml of dry tetrahydrofuran was stirred and cooled at -78° C. (dry-ice, acetone), under nitrogen and 2.17 g of sodium hydride (60% dispersion in mineral oil) was added. The mixture was stirred at -78° C. for 30 minutes, then 4.84 g of 1,1'-thiocarbonyldiimidazole was added in one portion. The temperature was kept at -78° C. for 2 hours, then was allowed to warm slowly to room temperature while stirring was continued for 48 hours. The reaction mixture was quenched with 500 ml of water and neutralized to pH 6-7 with 5% aqueous hydrochloric acid. A crystalline solid formed which was collected by filtration, triturated with ether, filtered and dried to give 3.2 g of the desired product as white crystals, m.p. 289°-291° C.

Workup

  1. stirringThe mixture was stirred at -78° C. for 30 minutes
  2. stirringwhile stirring
  3. waitwas continued for 48 hours
  4. customThe reaction mixture was quenched with 500 ml of water and neutralized to pH 6-7 with 5% aqueous hydrochloric acid
  5. customA crystalline solid formed which
  6. filtrationwas collected by filtration
  7. customtriturated with ether
  8. filtrationfiltered
  9. customdried

Sources & evidence

ORD record
ord-56555e23947645d8ac4605613af2489b
Source dataset
uspto-grants-1990_04
Patent number
US04916137

Reaction notes

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