Carbon Dioxide → HCID 21195145, compound

HRID 1067891Notes

Reaction equation

HRID 1067891 reaction equation
Br[C:2]1[N:7]=[C:6]([C:8]2[CH:13]=[C:12]([C:14]3[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=3)[CH:11]=[C:10]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=3)[N:9]=2)[CH:5]=[CH:4][CH:3]=1.C([Li])CCC.[C:33](=[O:35])=[O:34]>C1COCC1>[CH3:21][O:20][C:17]1[CH:18]=[CH:19][C:14]([C:12]2[CH:11]=[C:10]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=3)[N:9]=[C:8]([C:6]3[CH:5]=[CH:4][CH:3]=[C:2]([C:33]([OH:35])=[O:34])[N:7]=3)[CH:13]=2)=[CH:15][CH:16]=1

Participants

5

Reactant 3

HCID 280Carbon DioxideHCID 21195132HCID 21195132, compound2×HCID 178418339Butyllithium

Product 1

HCID 21195145HCID 21195145, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A flame dried 3 necked 1 L flask equipped with a mechanical stirrer, pressure equalizing addition funnel, and, attached via silicone rubber tubing, a Gooch tube containing solid 6-bromo-4′-(4-methoxyphenyl)-2,2′:6′2″-terpyridine (42.2 mmole) under nitrogen is charged with 400 mL THF and cooled in a Dry Ice/ether bath to −78° C. A solution of n-butyllithium (20 mL of 2.5 M) is transferred via nitrogen pump to the pressure equalizing addition funnel, and is then added to the THF solution. After stirring 15 minutes at −78° C., the solid 6-bromo-4′-(4-methoxyphenyl)-2,2′:6′2″-terpyridine is added portionwise over an 11 minute period from the Gooch tube. The temperature is not allowed to exceed −75° C. during the addition. After the addition, the bath is lowered, and the reaction mixture is allowed to warm slightly to −70° C. over a 10 minute period. The solution is re-cooled to −78° C., and the reaction mixture is transferred via cannula under nitrogen to a jacketed addition funnel cooled to −78° C. This anionic solution is maintained at −78° C. under nitrogen while it is added with stirring to 400 mL of THF saturated with anhydrous carbon dioxide in a 3 liter 3 necked flask attached to a silicone oil bubbler. Additional anhydrous carbon dioxide is slowly bubbled into the reaction mixture during the addition while the temperature is carefully controlled to remain below −70° C. After stirring for 60 minutes, the cooling bath is removed and the reaction mixture is carefully quenched with 100 ml of a 1 N aqueous HCl solution over a ten minute period. The reaction mixture is allowed to stir and warm to room temperature. The solvent is evaporated under vacuum below 20° C., the crude product is triturated with isopropanol, isolated by filtration, washed with ether and dried under vacuum.

Workup

  1. customA flame dried 3 necked 1 L flask
  2. customequipped with a mechanical stirrer
  3. additionaddition funnel
  4. additionaddition funnel
  5. additionto exceed −75° C. during the addition
  6. additionAfter the addition
  7. temperatureto warm slightly to −70° C. over a 10 minute period
  8. temperatureThe solution is re-cooled to −78° C.
  9. additionthe reaction mixture is transferred via cannula under nitrogen to a jacketed addition funnel
  10. temperaturecooled to −78° C
  11. temperatureThis anionic solution is maintained at −78° C. under nitrogen while it
  12. additionis added
  13. customAdditional anhydrous carbon dioxide is slowly bubbled into the reaction mixture during the addition while the temperature
  14. customto remain below −70° C
  15. stirringAfter stirring for 60 minutes
  16. customthe cooling bath is removed
  17. customthe reaction mixture is carefully quenched with 100 ml of a 1 N aqueous HCl solution over a ten minute period
  18. stirringto stir
  19. temperaturewarm to room temperature
  20. customThe solvent is evaporated under vacuum below 20° C.
  21. customthe crude product is triturated with isopropanol
  22. customisolated by filtration
  23. washwashed with ether
  24. customdried under vacuum

Sources & evidence

ORD record
ord-448b23a68e7642a2b8cf8857506ab530
Source dataset
uspto-grants-2001_06
Patent number
US06248870B1

Reaction notes

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