Phosphorus oxychloride → 6-Bromo-2-chloroquinoline-3-carbonitrile

HRID 986007Notes

Reaction equation

HRID 986007 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=O)[C:6]([C:13]#[N:14])=[CH:5]2.P(Cl)(Cl)([Cl:17])=O>>[Cl:17][C:7]1[C:6]([C:13]#[N:14])=[CH:5][C:4]2[C:9](=[CH:10][CH:11]=[C:2]([Br:1])[CH:3]=2)[N:8]=1

Participants

3

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 142210276-Bromo-2-oxo-1,2-dihydroquinoline-3-carbonitrile

Product 1

HCID 170398056-Bromo-2-chloroquinoline-3-carbonitrile

Procedure

6-Bromo-3-cyano-2-[1H]-quinolone (142 g) was heated under reflux in phosphorus oxychloride (500 cm3) for 1.5 hours. Volatile material was removed in vacuo and the solid residue was taken into chloroform (400 cm3) and the resulting slurry was poured onto ice. The mixture was neutralised with aqueous ammonia solution (S.G. 0.880) and the aqueous phase was extracted further with chloroform (2×150 cm3). The dried (MgSO4) organic extracts were concentrated in vacuo and the residue chromatographed on silica (Merck "MK 60.9385") eluting with toluene to give a solid which was recrystallised from ethyl acetate to afford 2-chloro-6-bromo-3-cyano-quinoline, m.p. 228°-230°, (80 g).

Workup

  1. customVolatile material was removed in vacuo
  2. additionthe resulting slurry was poured onto ice
  3. extractionthe aqueous phase was extracted further with chloroform (2×150 cm3)
  4. dry with materialThe dried (MgSO4) organic extracts
  5. concentrationwere concentrated in vacuo
  6. customthe residue chromatographed on silica (Merck "MK 60.9385")
  7. washeluting with toluene
  8. customto give a solid which
  9. customwas recrystallised from ethyl acetate

Sources & evidence

ORD record
ord-32e46682a1d04aa383aa29342a967e7c
Source dataset
uspto-grants-1987_12
Patent number
US04710507

Reaction notes

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