Pyridine → HCID 21082446, compound

HRID 1295917Notes

Reaction equation

HRID 1295917 reaction equation
C(Cl)(Cl)(Cl)Cl.[C:6]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)(=O)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[C:20]([O:27][CH3:28])(=[O:26])[CH2:21][C:22]([O:24][CH3:25])=[O:23].N1C=CC=C[CH:30]=1>O1CCCC1.[Ti](Cl)(Cl)(Cl)Cl.C(OCC)(=O)C.O>[C:7]1([CH:6]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:30]=[C:21]([C:20]([O:27][CH3:28])=[O:26])[C:22]([O:24][CH3:25])=[O:23])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

9

Reactant 4

HCID 1049PyridineHCID 3102BenzophenoneHCID 5943Carbon TetrachlorideHCID 7943Dimethyl malonate

Product 1

HCID 21082446HCID 21082446, compound

Reagents, catalysts & solvents 4

HCID 24193Titanium TetrachlorideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of titanium tetrachloride (22 mL, 0.2 mol), carbon tetrachloride (50 mL) and tetrahydrofuran (400 mL) at 0° C. is added benzophenone (18.2 g, 0.1 mol) and dimethyl malonate (13.3 g, 0.1 mol). After stirring at 0° C. for forty minutes, a solution of pyridine (32 mL) in tetrahydrofuran (70 mL) is added dropwise. The mixture is allowed to warm to room temperature and is then stirred for four days. The formation of a heavy precipitate requires the addition of more tetrahydrofuran to facilitate stirring. Water (100 mL) and ethyl acetate (100 mL) are then added. The mixtures separates into two layers. The aqueous layer is extracted with additional ethyl acetate. The combined organic layers are washed with brine, sodium bicarbonate and more brine. The solution is then dried over anhydrous magnesium sulfate and concentrated. The crude material is a white semi-solid slurry which is then recrystallized twice from heptane/ethyl acetate to afford 11.3 g of the title compound as a white solid melting at 120–122° C.

Workup

  1. temperatureto warm to room temperature
  2. stirringis then stirred for four days
  3. stirringto facilitate stirring
  4. extractionThe aqueous layer is extracted with additional ethyl acetate
  5. washThe combined organic layers are washed with brine, sodium bicarbonate and more brine
  6. dry with materialThe solution is then dried over anhydrous magnesium sulfate
  7. concentrationconcentrated
  8. customis then recrystallized twice from heptane/ethyl acetate

Sources & evidence

ORD record
ord-52e89435bf3448c996293b56cf5c165a
Source dataset
uspto-grants-2007_07
Patent number
US07244776B2

Reaction notes

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