Potassium tert-butoxide → HCID 178419785, compound

HRID 1432797Notes

Reaction equation

HRID 1432797 reaction equation
C([N:8]1[C:15]2[CH:14]3[CH2:16][CH:13]3[CH2:12][C:11]=2[C:10]([C:17]2[N:18]=[N:19][NH:20][N:21]=2)=[N:9]1)C1C=CC=CC=1.CC([O-])(C)C.[K+]>C1COCC1.CS(C)=O>[N:21]1[NH:20][N:19]=[N:18][C:17]=1[C:10]1[NH:9][N:8]=[C:15]2[C:11]=1[CH2:12][C@H:13]1[CH2:16][C@H:14]12

Participants

5

Reactant 2

HCID 23665647Potassium tert-butoxideHCID 69059203HCID 69059203, compound

Product 1

HCID 178419785HCID 178419785, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8028TetrahydrofuranSolvent

Procedure

Air was bubbled through a stirring solution of 2-benzyl-4-(2H-tetrazol-5-yl)-1a,2,5,5a-tetrahydro-1H-2,3-diaza-cyclopropa[a]pentalene (10.4 g, 37.4 mmol) and KOt-Bu (374 mL of a 1M solution in THF, 374 mmol) in DMSO (300 mL) for 20 h at rt. The remaining THF was removed in vacuo and the reaction was acidified to pH=2 by the addition of HCl (3M aq). The mixture was concentrated in vacuo to near dryness. The residue was dissolved in HCl (1N aq., 250 mL) and extracted with EtOAc (5×250 mL). The organics were dried over MgSO4, filtered, and concentrated. The product was purified and converted to the ammonium salt by loading material (as a solution in MeOH) on to a column containing Bondesil SCX SPE resin (˜250 g). The column was flushed with MeOH (200 mL) to remove unbound impurities. The product was eluted using 2N NH3/MeOH (approx. 200 mL). Concentration of the basic eluant yielded the ammonium salt of Compound 4 as a white solid. 1H NMR (400 MHz, MeOD): δ 3.02 (1H, dd, J=16.4, 6.0 Hz), 2.90 (1H, d, J=16.0 Hz), 2.19 (2H, m), 1.17 (1H, m), 0.33 (1H, m). HPLC/MS: Discovery® C18 column (5 μ, 50×2.1 mm), 5% v/v CH3CN (containing 1% v/v TFA) in H2O (containing 1% v/v TFA) gradient to 99% v/v CH3CN in H2O, 0.75 mL/min, tr=1.21 min, ESI+=189.0 (M+H). [α]25D+35.7 (c 0.39, MeOH).

Workup

  1. customThe remaining THF was removed in vacuo
  2. additionthe reaction was acidified to pH=2 by the addition of HCl (3M aq)
  3. concentrationThe mixture was concentrated in vacuo
  4. dissolutionThe residue was dissolved in HCl (1N aq., 250 mL)
  5. extractionextracted with EtOAc (5×250 mL)
  6. dry with materialThe organics were dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe product was purified
  10. additioncontaining Bondesil SCX SPE resin (˜250 g)
  11. customThe column was flushed with MeOH (200 mL)
  12. customto remove unbound impurities
  13. washThe product was eluted

Sources & evidence

ORD record
ord-be8e77b6e7be4cdaa7aca5e21afb9665
Source dataset
uspto-grants-2009_11
Patent number
US07612106B2

Reaction notes

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