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

HRID 393327

Reaction equation

HRID 393327 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-e99686eefb464ae38cbda4bc7b8092c7
Source dataset
uspto-grants-2004_10
Patent number
US06806288B1

Linked notes

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