Carbon Dioxide → Ammonia

HRID 450947Notes

Reaction equation

HRID 450947 reaction equation
C([Li])CCC.Br[C:7]1[CH:8]=[C:9]([CH:38]=[CH:39][CH:40]=1)[CH2:10][O:11][CH:12]1[CH2:17][CH2:16][N:15]([C:18]([CH3:37])([CH3:36])[CH2:19][CH2:20][C:21]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:22]#[N:23])[CH2:14][CH2:13]1.C(=O)=O>O1CCCC1>[NH3:15].[CH2:10]([O:11][CH:12]1[CH2:13][CH2:14][N:15]([C:18]([CH3:37])([CH3:36])[CH2:19][CH2:20][C:21]([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:22]#[N:23])[CH2:16][CH2:17]1)[C:9]1[CH:8]=[CH:7][CH:40]=[CH:39][CH:38]=1

Participants

6

Reactant 3

HCID 280Carbon DioxideHCID 59423969HCID 59423969, compoundHCID 178418339Butyllithium

Product 2

HCID 222AmmoniaHCID 59423905HCID 59423905, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

n-Butyl lithium (2.5M in hexanes, 0.23 mL, 0.56 mmol) was added dropwise to a solution of the product of example 87 (200 mg, 0.38 mmol) in tetrahydrofuran (8 mL), cooled to −78° C., and the mixture was stirred for 30 minutes. Carbon dioxide was then passed through the solution, with stirring at −78° C., for 3.5 hours before the mixture was allowed to warm to room temperature. The reaction mixture was concentrated in vacuo and the residue was partitioned between ethyl acetate (30 mL) and water (20 mL). The organic layer was separated, washed with water, dried over magnesium sulfate and concentrated in vacuo. Purification of the residue by column chromatography on silica gel, eluting with dichloromethane:methanol:0.88 ammonia, 100:0:0 to 98:2:0.2, afforded the title compound as a by-product, as an off white solid in 68% yield, 116 mg.

Workup

  1. stirringwith stirring at −78° C., for 3.5 hours before the mixture
  2. temperatureto warm to room temperature
  3. concentrationThe reaction mixture was concentrated in vacuo
  4. customthe residue was partitioned between ethyl acetate (30 mL) and water (20 mL)
  5. customThe organic layer was separated
  6. washwashed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customPurification of the residue by column chromatography on silica gel
  10. washeluting with dichloromethane

Sources & evidence

ORD record
ord-667d76fe9ecd4c8e99ebe711f4e6368e
Source dataset
uspto-grants-2013_07
Patent number
US08486992B2

Reaction notes

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