3-Chloro-1-propyne → 9-Chloro-2-methyl-6-prop-2-ynyl-2,6,8,10-tetrazabicyclo[5.4.0]undeca-7,9,11-trien-3-one

HRID 2234431Notes

Reaction equation

HRID 2234431 reaction equation
[H-].[Na+].[Cl:3][C:4]1[N:14]=[C:13]2[C:7]([N:8]([CH3:16])[C:9](=[O:15])[CH2:10][CH2:11][NH:12]2)=[CH:6][N:5]=1.[CH2:17](Cl)[C:18]#[CH:19]>CC(N(C)C)=O>[Cl:3][C:4]1[N:14]=[C:13]2[C:7](=[CH:6][N:5]=1)[N:8]([CH3:16])[C:9](=[O:15])[CH2:10][CH2:11][N:12]2[CH2:19][C:18]#[CH:17]

Participants

5

Reactant 3

HCID 122213-Chloro-1-propyneHCID 24758Sodium hydrideHCID 866175762-Chloro-5-methyl-5,7,8,9-tetrahydro-6H-pyrimido[4,5-b][1,4]diazepin-6-one2×

Product 1

HCID 866175499-Chloro-2-methyl-6-prop-2-ynyl-2,6,8,10-tetrazabicyclo[5.4.0]undeca-7,9,11-trien-3-oneYield 67%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent2×

Procedure

To a cooled (ice/water bath) suspension of sodium hydride (60% dispersion in mineral oil; 15 mg, 0.38 mmol) in DMA (1 mL) was carefully added a solution of 10-chloro-6-methyl-2,6,9,11-tetrazabicyclo[5.4.0]undeca-7,9,11-trien-5-one (Intermediate 100; 65 mg, 0.31 mmol) in DMA (1.5 mL). The reaction mixture was allowed to stir, under nitrogen, on an ice bath for 1 hour prior to addition of propargyl chloride (34 mg, 0.47 mmol). The reaction mixture was left to stir at ambient temperature overnight and then quenched by addition of saturated aqueous ammonium chloride solution (0.5 mL) and stirred for 15 minutes. The resultant mixture was partitioned between DCM (10 mL) and water (10 mL). The organic phase was separated by filtration through PTFE filter cup. The aqueous phase was re-extracted with DCM (5 mL) and the combined organic solutions evaporated to dryness to yield the title compound as a beige coloured solid (52 mg, 67%)

Workup

  1. temperatureTo a cooled
  2. waitThe reaction mixture was left
  3. stirringto stir at ambient temperature overnight
  4. customquenched by addition of saturated aqueous ammonium chloride solution (0.5 mL)
  5. stirringstirred for 15 minutes
  6. customThe resultant mixture was partitioned between DCM (10 mL) and water (10 mL)
  7. customThe organic phase was separated by filtration through PTFE
  8. filtrationfilter cup
  9. extractionThe aqueous phase was re-extracted with DCM (5 mL)
  10. customthe combined organic solutions evaporated to dryness

Sources & evidence

ORD record
ord-95460966ebcb4aaa9c531d14eb17daa2
Source dataset
uspto-grants-2010_05
Patent number
US07709471B2

Reaction notes

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