Triethyl phosphite → HCID 86610184, compound

HRID 252793Notes

Reaction equation

HRID 252793 reaction equation
[I-].Br[C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[N+:8]([CH2:12][CH3:13])=[C:7]([CH3:14])[C:6]2([CH3:16])[CH3:15].[CH2:17]([O:19][P:20]([O:24]CC)[O:21][CH2:22][CH3:23])[CH3:18]>[Ni](Cl)Cl.CO>[CH2:17]([O:19][P:20]([C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[N:8]([CH2:12][CH3:13])[C:7](=[CH2:14])[C:6]2([CH3:16])[CH3:15])(=[O:24])[O:21][CH2:22][CH3:23])[CH3:18]

Participants

5

Reactant 2

HCID 31215Triethyl phosphiteHCID 67262703HCID 67262703, compound

Product 1

HCID 86610184HCID 86610184, compoundYield 62%

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalyst2×HCID 887MethanolSolvent

Conditions

Temperature
175 °C

Procedure

To a 250 mL flask were added 3 (9.6 g, 20 mmol) and nickel chloride (0.52 g, 4.0 mmol). The flask was fitted with a dropping funnel and a condenser and was then lowered into an oil bath. The mixture was heated to 175° C. At approx. 165° C. triethylphosphite (15 mL, 86 mmol) was added dropwise. The mixture fizzed and became dark before turning to a dark straw color. After heating at 175° C. for 30 min a second portion of nickel chloride (0.52 g, 4.0 mmol) was added. The mixture fizzed vigorously, gave off much vapor and became dark grey-green in color. Heating was continued for 30 min and then the reaction was cooled to rt. The mixture was treated with methanol (100 mL) and filtered through a bed of celite. The methanol was evaporated in vacuo to leave an oil that was fractionally distilled on a KUGELROHR® vacuum distillation apparatus to afford 5 as a colorless liquid (4.0 g, 62%). The oil was stored under argon.

Workup

  1. customThe flask was fitted with a dropping funnel and a condenser
  2. customwas then lowered into an oil bath
  3. additionwas added
  4. customgave off much vapor
  5. temperatureHeating
  6. temperaturethe reaction was cooled to rt
  7. filtrationfiltered through a bed of celite
  8. customThe methanol was evaporated in vacuo
  9. customto leave an oil that
  10. distillationwas fractionally distilled on a KUGELROHR® vacuum distillation apparatus

Sources & evidence

ORD record
ord-46a4bbee36ad4552b221a66ef03e7941
Source dataset
uspto-grants-2011_01
Patent number
US07868157B2

Reaction notes

Loading…