Pyridine → HCID 10850422, compound

HRID 2260698Notes

Reaction equation

HRID 2260698 reaction equation
N1C=CC=CC=1.[CH3:7][C:8]1[C:13](=O)[C:12]([CH3:15])=[C:11]([CH3:16])[C:10](=[O:17])[C:9]=1[CH2:18][C:19]([CH3:21])=[CH2:20].[NH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.S(S([O-])=O)([O-])=O.[Na+].[Na+]>ClCCCl.O.[Ti](Cl)(Cl)(Cl)Cl>[CH3:7][C:8]1[C:9]([CH2:18][C:19]([CH3:21])=[CH2:20])=[C:10]([OH:17])[C:11]([CH3:16])=[C:12]([CH3:15])[C:13]=1[NH:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 6115AnilineHCID 24489Sodium DithioniteHCID 3188402,3,5-Trimethyl-6-(2-methylprop-2-en-1-yl)cyclohexa-2,5-diene-1,4-dione

Product 1

HCID 10850422HCID 10850422, compoundYield 42.8%

Reagents, catalysts & solvents 3

HCID 24193Titanium TetrachlorideCatalystHCID 111,2-DichloroethaneSolvent2×HCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

Titanium tetrachloride (2 58 ml 23 4 mmol) was added dropwise to a solution of pyridine (7.60 ml, 93.6 mmol) in 1,2-dichloroethane (40 ml) and, after completion of the addition, the reaction mixture was heated under reflux for 30 minutes in an argon atmosphere. After cooling of the reaction mixture, a solution of 3,5,6-trimethyl-2-(2-methyl-2-propenyl)-1,4-benzoquinone (2.40 g, 11.7 mmol) and aniline (3.35 ml, 35.1 mmol) in 1,2-dichloroethane (5 ml) was added thereto and the mixture was stirred at 90° C. for 2 hours in an argon atmosphere. The reaction mixture was cooled and filtered through Cerite and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate, 98:2). The resulting compound was dissolved in tetrahydrofuran (10 ml) and to the solution was added a solution of sodium hydrosulfite (12 g, 69 mmol) in water (30 ml). The mixture was stirred at room temperature for 30 minutes. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The extract was combined with the organic phase and the mixture was washed with water and dried and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (hexaneethyl acetate, 95:5) to obtain the desired compound as oil (1.41 g, yield: 42.8%).

Workup

  1. additionafter completion of the addition
  2. temperaturethe reaction mixture was heated
  3. temperatureunder reflux for 30 minutes in an argon atmosphere
  4. temperatureAfter cooling of the reaction mixture
  5. temperatureThe reaction mixture was cooled
  6. filtrationfiltered through Cerite
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (hexane-ethyl acetate, 98:2)
  9. dissolutionThe resulting compound was dissolved in tetrahydrofuran (10 ml) and to the solution
  10. stirringThe mixture was stirred at room temperature for 30 minutes
  11. customThe organic phase was separated
  12. extractionthe aqueous phase was extracted with ethyl acetate
  13. washthe mixture was washed with water
  14. customdried
  15. distillationthe solvent was distilled off under reduced pressure
  16. customThe residue was purified by silica gel chromatography (hexaneethyl acetate, 95:5)

Sources & evidence

ORD record
ord-e98ac11488cc4797b7ebaf5db5299615
Source dataset
uspto-grants-1995_12
Patent number
US05478844

Reaction notes

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