2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 67195229, compound

HRID 1853261Notes

Reaction equation

HRID 1853261 reaction equation
COC(C1N=CC2C(C=1)=CC(OC)=C(OC)C=2)=O.[CH3:19][O:20][C:21]([CH:23]1[CH2:32][C:31]2[C:26](=[CH:27][CH:28]=[CH:29][C:30]=2[Br:33])[CH2:25][NH:24]1)=[O:22].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCCC1>[Br:33][C:30]1[CH:29]=[CH:28][CH:27]=[C:26]2[C:31]=1[CH:32]=[C:23]([C:21]([O:20][CH3:19])=[O:22])[N:24]=[CH:25]2

Participants

5

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 11096910HCID 11096910, compoundHCID 44890925Methyl 5-bromo-1,2,3,4-tetrahydroisoquinoline-3-carboxylate

Product 1

HCID 67195229HCID 67195229, compoundYield 91.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

methyl-5-bromo-isoquinoline-3-carboxylate was prepared using the following procedure describe in US054777252 for methyl-6,7-dimethoxy-isoquinoline-3-carboxylate: 5-bromo-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid methyl ester (880 mg, 3.26 mmol) was treated with 2,3-Dichloro-5,6-dicyanobenzoquinone (1.62 mg, 7.19 mmol) in dry tetrahydrofuran (19 ml) at reflux temperature for 18 hours. The cooled dark mixture was filtered and the solid washed with dichloromethane. The filtrate was treated with a 1M aqueous sodium hydroxide solution and the aqueous layer was extracted twice with dichloromethane. The organic layer was washed with water, brine, dried over sodium sulfate and concentrated to dryness. The residue was purified by flash chromatography over silica gel (gradient cyclohexane/ethyl acetate: 0-100%) to yield methyl 5-bromo-isoquinoline-3-carboxylate (793 mg, 91%) as beige solid.

Workup

  1. custommethyl-5-bromo-isoquinoline-3-carboxylate was prepared
  2. temperatureat reflux temperature for 18 hours
  3. filtrationThe cooled dark mixture was filtered
  4. washthe solid washed with dichloromethane
  5. additionThe filtrate was treated with a 1M aqueous sodium hydroxide solution
  6. extractionthe aqueous layer was extracted twice with dichloromethane
  7. washThe organic layer was washed with water, brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated to dryness
  10. customThe residue was purified by flash chromatography over silica gel (gradient cyclohexane/ethyl acetate: 0-100%)

Sources & evidence

ORD record
ord-763072794b574f3fb996cf382cfe8ce2
Source dataset
uspto-grants-2015_02
Patent number
US08962627B2

Reaction notes

Loading…