Boron Trichloride → HCID 59224693, compound

HRID 1811716Notes

Reaction equation

HRID 1811716 reaction equation
C([O:8][C:9]1[CH:10]=[CH:11][C:12]([CH3:23])=[C:13]([C:15]2[CH:20]=[C:19]([Cl:21])[N:18]=[C:17]([NH2:22])[N:16]=2)[CH:14]=1)C1C=CC=CC=1.ClB(Cl)Cl.C(=O)(O)[O-].[Na+]>ClCCl>[NH2:22][C:17]1[N:16]=[C:15]([C:13]2[CH:14]=[C:9]([OH:8])[CH:10]=[CH:11][C:12]=2[CH3:23])[CH:20]=[C:19]([Cl:21])[N:18]=1

Participants

5

Reactant 3

HCID 25135Boron TrichlorideHCID 516892Sodium BicarbonateHCID 59224670HCID 59224670, compound

Product 1

HCID 59224693HCID 59224693, compoundYield 71.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

4-(5-Benzyloxy-2-methylphenyl)-6-chloropyrimidin-2-ylamine (12.5 g, 38.4 mmol) obtained in Step 3 above was placed in a reaction vessel, and then dichloromethane (500 ml) was added thereto. The resulting solution was cooled to 0° C. Then, a dichloromethane solution of 1.0 M trichloroborane was added dropwise over 30 minutes. The mixture was stirred at 0° C. for 1 hour, and diluted with dichloromethane (1500 ml). A saturated aqueous sodium bicarbonate solution (2000 ml) was added, and the mixture was warmed to room temperature. The organic layer was separated, and then sequentially washed with water (1500 ml) and a saturated aqueous sodium chloride solution (1000 ml). The aqueous layer was extracted with ethyl acetate (3000 ml), and the ethyl acetate solution was sequentially washed with water (1500 ml) and a saturated aqueous sodium chloride solution (1000 ml). The washed organic layers were combined together, and dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (developing solvent: n-hexane:ethyl acetate=2:1) to yield 3-(2-amino-6-chloropyrimidin-4-yl)-4-methylphenol (6.45 g, 71%) as a white solid material.

Workup

  1. temperaturethe mixture was warmed to room temperature
  2. customThe organic layer was separated
  3. washsequentially washed with water (1500 ml)
  4. extractionThe aqueous layer was extracted with ethyl acetate (3000 ml)
  5. washthe ethyl acetate solution was sequentially washed with water (1500 ml)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationAfter filtration
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. customThe resulting crude product was purified by silica gel column chromatography (developing solvent: n-hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-cf82a6215ec147adbd0eb961f1f5f2f9
Source dataset
uspto-grants-2013_01
Patent number
US08362236B2

Reaction notes

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