Boron Trichloride → 4-Chloro-7-hydroxy-6-methoxyquinoline-3-carbonitrile

HRID 1595714Notes

Reaction equation

HRID 1595714 reaction equation
C([O:8][C:9]1[CH:18]=[C:17]2[C:12]([C:13]([Cl:21])=[C:14]([C:19]#[N:20])[CH:15]=[N:16]2)=[CH:11][C:10]=1[O:22][CH3:23])C1C=CC=CC=1.B(Cl)(Cl)Cl>C(Cl)Cl>[Cl:21][C:13]1[C:12]2[C:17](=[CH:18][C:9]([OH:8])=[C:10]([O:22][CH3:23])[CH:11]=2)[N:16]=[CH:15][C:14]=1[C:19]#[N:20]

Participants

4

Reactant 2

HCID 25135Boron TrichlorideHCID 224666467-(Benzyloxy)-4-chloro-6-methoxyquinoline-3-carbonitrile

Product 1

HCID 1357436694-Chloro-7-hydroxy-6-methoxyquinoline-3-carbonitrileYield 19.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A stirred suspension of 0.54 g of 7-benzyloxy-4-chloro-6-methoxy-quinoline-3-carbonitrile in 10 ml of methylene chloride was cooled to 0° C. To this was added 10 ml of boron trichloride (1M in methylene chloride). The mixture darkened as it warmed to room temperature and a solid precipitated out. After stirring for 1 hour, no further reaction was observed. The solid (unreacted starting material) was filtered off, the remaining solution was cooled to 0° C. and quenched by the dropwise addition of methanol. Following evaporation of the solvent, the residue was dissolved in methylene chloride/methanol/acetone. Purification of this residue was carried out using silica gel chromatography, eluting with a solvent gradient of 1 to 5 percent methanol/methylene chloride, to provide 0.075 g of 4-chloro-7-hydroxy-6-methoxy-quinoline-3-carbonitrile as a yellow solid, dec>245° C.; mass spectrum (electrospray, m/e) M+H 235.2.

Workup

  1. temperaturewarmed to room temperature
  2. customa solid precipitated out
  3. customno further reaction
  4. filtrationThe solid (unreacted starting material) was filtered off
  5. temperaturethe remaining solution was cooled to 0° C.
  6. customquenched by the dropwise addition of methanol
  7. customevaporation of the solvent
  8. dissolutionthe residue was dissolved in methylene chloride/methanol/acetone
  9. customPurification of this residue
  10. washeluting with a solvent gradient of 1 to 5 percent methanol/methylene chloride

Sources & evidence

ORD record
ord-31f15a7774a84af99510547488c3df2d
Source dataset
uspto-grants-2001_09
Patent number
US06288082B1

Reaction notes

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