Undec-4-ene → Ethyl 6-iodo-1,2-dihydro-2-(trifluoromethyl)-3-quinolinecarboxylate

HRID 1636662Notes

Reaction equation

HRID 1636662 reaction equation
[I:1][C:2]1[CH:3]=[CH:4][C:5]([NH2:10])=[C:6]([CH:9]=1)[CH:7]=O.CCCCCCC=CCCC.[F:22][C:23]([F:32])([F:31])/[CH:24]=[CH:25]/[C:26]([O:28][CH2:29][CH3:30])=[O:27]>CN1CCCN(C)C1=O>[I:1][C:2]1[CH:9]=[C:6]2[C:5](=[CH:4][CH:3]=1)[NH:10][CH:24]([C:23]([F:22])([F:32])[F:31])[C:25]([C:26]([O:28][CH2:29][CH3:30])=[O:27])=[CH:7]2

Participants

5

Reactant 3

HCID 136496Undec-4-eneHCID 5371261Ethyl (2E)-4,4,4-trifluoro-2-butenoateHCID 142210302-Amino-5-iodobenzaldehyde

Product 1

HCID 21883508Ethyl 6-iodo-1,2-dihydro-2-(trifluoromethyl)-3-quinolinecarboxylateYield 50.3%

Reagents, catalysts & solvents 1

HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Conditions

Temperature
60 °C

Procedure

A mixture of 5-iodo-2-aminobenzaldehyde (24.0 g, 96.7 mmol), diazbicyclo[2.2.2]-undec-7-ene (32.2 g, 212.0 mmol), and ethyl 4,4,4-trifluorocrotonate (35.7 g, 212.0 mmol) in 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (48 mL) was heated at 60° C. for 8 hours. The solution was cooled to room temperature and the solution poured into ethyl acetate-hexanes (1:1, 500 mL). The solution was extracted with 2.5 N aqueous hydrochloric acid (2×200 mL), saturated aqueous ammonium chloride (2×200 mL), dried over sodium sulfate, filtered and concentrated in vacuo. The resulting dark yellow oil was dissolved in hexanes (100 mL) and fine yellow crystals formed upon standing. Vacuum filtration of this suspension yielded ethyl 6-iodo-1,2-dihydro-2-(trifluoromethyl)-3-quinolinecarboxylate as fine yellow crystals (19.3 g, 50% yield): mp 137-138° C. 1H NMR (CDCl3, 300 MHz) 7.62 (s, 1H), 7.36-7.48 (m, 2H), 6.43 (d, J=8.2 Hz), 5.36 (brs, 1H), 5.11 (q, 1H, J=7.1 Hz), 4.25-4.35 (m, 2H), 1.34 (t, 3H, J=7.0 Hz). ESHRMS m/z 395.9716 (M-H, Calc'd 395.9708).

Workup

  1. temperatureThe solution was cooled to room temperature
  2. extractionThe solution was extracted with 2.5 N aqueous hydrochloric acid (2×200 mL), saturated aqueous ammonium chloride (2×200 mL)
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. dissolutionThe resulting dark yellow oil was dissolved in hexanes (100 mL)
  7. customfine yellow crystals formed
  8. filtrationVacuum filtration of this suspension

Sources & evidence

ORD record
ord-88e4574d0afd42948676c959d74c0385
Source dataset
uspto-grants-2000_03
Patent number
US06034256

Reaction notes

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