HCID 178498128, compound → Methyl 2-(4-chloro-3-nitrophenyl)-4-hydroxy-3,3-dimethyl-1,2,3,4-tetrahydroquinoline-6-carboxylate

HRID 1801272Notes

Reaction equation

HRID 1801272 reaction equation
[Cl:1][C:2]1[CH:19]=[CH:18][C:5](/[CH:6]=[N:7]/[C:8]2[CH:17]=[CH:16][C:11]([C:12]([O:14][CH3:15])=[O:13])=[CH:10][CH:9]=2)=[CH:4][C:3]=1[N+:20]([O-:22])=[O:21]>O1CCCC1.FC(F)(F)S([O-])(=O)=O.[Y+3].FC(F)(F)S([O-])(=O)=O.FC(F)(F)S([O-])(=O)=O>[Cl:1][C:2]1[CH:19]=[CH:18][C:5]([CH:6]2[C:11]([CH3:16])([CH3:10])[CH:12]([OH:13])[C:17]3[C:8](=[CH:9][CH:10]=[C:11]([C:12]([O:14][CH3:15])=[O:13])[CH:16]=3)[NH:7]2)=[CH:4][C:3]=1[N+:20]([O-:22])=[O:21]

Participants

4

Reactant 1

HCID 178498128HCID 178498128, compound

Product 1

HCID 67440905Methyl 2-(4-chloro-3-nitrophenyl)-4-hydroxy-3,3-dimethyl-1,2,3,4-tetrahydroquinoline-6-carboxylateYield 94.3%

Reagents, catalysts & solvents 2

HCID 2733939Yttrium trifluoromethanesulfonateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-chloro-3-nitrobenzaldehyde (5.0 g, 27 mmol) in 42 mL of ethonal was added methyl 4-aminobenzoate (4.07 g, 27 mmol), and the reaction mixture was stirred over weekend. The yellow precipitates were filtered, and 8.47 g of (E)-methyl 4-(4-chloro-3-nitrobenzylidenamino)benzoate a yellow solid was obtained. (Yield=98%). (E)-methyl 4-(4-chloro-3-nitrobenzylideneamino)benzoate (8.47 g, 26.6 mmol) and yttrium(III) trifluoromethanesulfonate (800 mg, 1.33 mmol) was dissolved in dry tetrahydrofuran (100 mL), and then cooled below 0° C. Isobutyl aldehyde (2.30 g, 31.9 mmol) was added below 0° C. The reaction mixture was stirred at room temperature overnight. Thin layer chromatography showed most of starting material was consumed. 50 mL of ethyl acetate and 50 mL of water were added to the mixture, and the separated organic layer was washed with brine again. The organic layer was dried over sodium sulfate and purified on silica gel to afford 4.9 g of methyl 2-(4-chloro-3-nitrophenyl)-4-hydroxy-3,3-dimethyl-1,2,3,4-tetrahydroquinoline-6-carboxylate. (Yield=47%). MS (ESI+APCI) M+1=373.

Workup

  1. temperaturecooled below 0° C
  2. customwas consumed
  3. addition50 mL of ethyl acetate and 50 mL of water were added to the mixture
  4. washthe separated organic layer was washed with brine again
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. custompurified on silica gel

Sources & evidence

ORD record
ord-ab75aaadd26e443ab12a472675b86bb2
Source dataset
uspto-grants-2013_01
Patent number
US08344137B2

Reaction notes

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