Pyridine → HCID 53640968, compound

HRID 1885232Notes

Reaction equation

HRID 1885232 reaction equation
N1C=CC=CC=1.[C:7]([O:16][CH3:17])(=[O:15])[C:8]1[C:9](=[CH:11][CH:12]=[CH:13][CH:14]=1)[NH2:10].[CH3:18][C:19]([C:22]1[C:23](=[O:33])[C:24]([C:29]([CH3:32])([CH3:31])[CH3:30])=[CH:25][C:26](=O)[CH:27]=1)([CH3:21])[CH3:20]>C(Cl)Cl.C1COCC1.[Ti](Cl)(Cl)(Cl)Cl.Cl[Ti](Cl)(Cl)Cl.N1C=CC=CC=1>[CH3:17][O:16][C:7](=[O:15])[C:8]1[CH:14]=[CH:13][CH:12]=[CH:11][C:9]=1[NH:10][C:26]1[CH:25]=[C:24]([C:29]([CH3:30])([CH3:31])[CH3:32])[C:23]([OH:33])=[C:22]([C:19]([CH3:21])([CH3:20])[CH3:18])[CH:27]=1

Participants

8

Reactant 3

HCID 1049PyridineHCID 8635Methyl AnthranilateHCID 128672,6-Di-t-butyl-p-benzoquinone

Product 1

HCID 53640968HCID 53640968, compound

Reagents, catalysts & solvents 4

HCID 24193Titanium TetrachlorideCatalystHCID 15805336HCID 15805336, compoundCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Titanium tetrachloride (28.8 mL, 1.0 M in CH2Cl2) is added dropwise to a stirred solution of pyridine (12.0 mL) in CH2Cl2 (100 mL) at 0° C. The resulting suspension is added to a solution of methyl anthranilate (6.8 g, 45.4 mmol) and 2,6-bis(1,1-dimethylethyl)-p-benzoquinone (10.0 g, 45.4 mol) in dry THF (200 mL). The reaction mixture is warmed to reflux under an argon atmosphere for four hours. At this time, another TiCl4 /pyridine suspension (prepared as above) is added. The reaction mixture is warmed at reflux for an additional 12 hours. It is cooled and filtered through Celite to remove the suspended solid. The solid is washed with ethyl acetate (100 mL) and the combined filtrates are evaporated. The residue is taken up in 200 mL of THF and stirred vigorously with a solution of sodium dithionite (100 g) in water (100 mL) for 30 minutes. The layers are separated and the aqueous layer is extracted with ethyl acetate (3×100 mL). The organic layers are combined, washed with brine (2×100 mL), dried over magnesium sulfate, and evaporated to give 2-[[(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)]amino]benzoic acid methyl ester; mp 155°-158° C.

Workup

  1. temperatureThe reaction mixture is warmed
  2. temperatureto reflux under an argon atmosphere for four hours
  3. temperatureThe reaction mixture is warmed
  4. temperatureat reflux for an additional 12 hours
  5. temperatureIt is cooled
  6. filtrationfiltered through Celite
  7. customto remove the suspended solid
  8. washThe solid is washed with ethyl acetate (100 mL)
  9. customthe combined filtrates are evaporated
  10. customThe layers are separated
  11. extractionthe aqueous layer is extracted with ethyl acetate (3×100 mL)
  12. washwashed with brine (2×100 mL)
  13. dry with materialdried over magnesium sulfate
  14. customevaporated

Sources & evidence

ORD record
ord-39f73afeea884312bdfd47ad1ea42a2e
Source dataset
uspto-grants-1992_09
Patent number
US05143929

Reaction notes

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