Carbon Dioxide → HCID 67403142, compound

HRID 468004Notes

Reaction equation

HRID 468004 reaction equation
[N+]([O-])(O)=O.[O:5]1[CH:10]=[CH:9][CH:8]=[C:7](O)[BH:6]1.C(#N)C.[C:15](=[O:17])=O.[N+:18]([C:21]1[CH:26]=CC=[CH:23][CH:22]=1)([O-:20])=[O:19]>>[CH3:10][CH:9]1[CH2:15][O:17][B:6]([OH:5])[C:7]2[CH:26]=[C:21]([N+:18]([O-:20])=[O:19])[CH:22]=[CH:23][C:8]1=2

Participants

6

Reactant 5

HCID 280Carbon DioxideHCID 944Nitric Acid2×HCID 6342AcetonitrileHCID 7416NitrobenzeneHCID 178516265HCID 178516265, compound

Product 1

HCID 67403142HCID 67403142, compound

Procedure

In a 100 ml round bottom flask, the fuming nitric acid was cooled to −45° C. using a dry ice/acetonitrile bath. 3.2054 g (10.2330 mmol, 1.0 eq) of the oxaborininol was dissolved in 2.5 mL of nitrobenzene. This solution was then added dropwise to the stirred and cooled nitric acid over a period of approximately 15 minutes. The reaction was allowed to stir for 45 minutes, recharging the acetonitrile and dry ice as needed. After 45 minutes, the reaction solution was poured over approximately 250 mL of wet ice. The mixture/suspension was allowed to warm to room temperature, stirring as it warmed (approximately 90 minutes). The aqueous mixture was then extracted with DCM (2×50 mL). The layers were separated and the organic layers were combined and washed with water to remove excess nitric acid (2×100 mL) until pH paper showed the water retained a neutral pH. The organic solution was then dried over MgSO4, filtered under vacuum, and then the solvent was removed under reduced pressure. The resultant yellow oil was then treated slowly with heptane, swirling as the solvent was added, until a yellow-white solid crashed out. The solid was then collected by filtration and washed with additional ice-cooled heptane. A yellow powder was isolated. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.99-1.47 (m, 4H) 3.14 (dd, J=10.98, 5.86 Hz, 1H) 3.88 (dt, J=11.21, 5.79 Hz, 1H) 4.13 (dd, J=11.03, 4.00 Hz, 1H) 7.57 (d, J=8.44 Hz, 1H) 8.27 (dd, J=8.42, 2.56 Hz, 1H) 8.48 (d, J=2.49 Hz, 1H) 8.95 (s, 1H).

Workup

  1. additionThis solution was then added dropwise to the
  2. stirringto stir for 45 minutes
  3. stirringstirring as it
  4. temperaturewarmed (approximately 90 minutes)
  5. extractionThe aqueous mixture was then extracted with DCM (2×50 mL)
  6. customThe layers were separated
  7. washwashed with water
  8. customto remove excess nitric acid (2×100 mL)
  9. dry with materialThe organic solution was then dried over MgSO4
  10. filtrationfiltered under vacuum
  11. customthe solvent was removed under reduced pressure
  12. additionThe resultant yellow oil was then treated slowly with heptane
  13. additionwas added, until a yellow-white solid
  14. filtrationThe solid was then collected by filtration
  15. washwashed with additional ice-
  16. temperaturecooled heptane
  17. customA yellow powder was isolated

Sources & evidence

ORD record
ord-e5971d242b364caba4a8a4a9daf508ee
Source dataset
uspto-grants-2014_01
Patent number
US08623911B2

Reaction notes

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