Benzaldehyde → HCID 81697470, compound

HRID 1486835Notes

Reaction equation

HRID 1486835 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][C:3]=1[C:9]([F:12])([F:11])[F:10].[Li]CCCC.CCCCCC.[CH:24](=[O:31])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.Cl>CCOCC.O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:24]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[OH:31])=[CH:4][C:3]=1[C:9]([F:12])([F:11])[F:10]

Participants

8

Reactant 5

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 8058HexaneHCID 121872191-Bromo-4-iodo-2-(trifluoromethyl)benzeneHCID 178418339Butyllithium

Product 1

HCID 81697470HCID 81697470, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

To a solution of 1-bromo-4-iodo-2-(trifluoromethyl)benzene (246 mg, 0.701 mmol) in 1.4 mL of Et2O (C=0.5M) was added dropwise a 1.6M solution of BuLi in hexane (460 μL, 1.05 eq) at −78° C. After 15 min of stirring, benzaldehyde (86 μL, 1.2 eq) was slowly added. The mixture was stirred for 4 h at −75° C. and then, hydrolyzed with water and with a 1M HCl solution to acidify. The layers were separated. The aqueous layer was extracted with DCM (3×10 mL). The combined organics were washed with brine, dried over MgSO4, filtered and solvents were removed in vacuo. The crude residue was purified by silica gel flash chromatography (cyclohexane/AcOEt 93:7 to 90:10) to afford the desired product in 76% yield (176 mg) as an uncoloured oil. 1H NMR (300 MHz, CDCl3) δ 7.76 (d, J=2.2 Hz, 1H), 7.65 (d, J=8.3 Hz, 1H), 7.41-7.27 (m, 6H), 5.81 (s, 1H), 2.36 (s, OH); 13C NMR (75 MHz, CDCl3) δ 143.5 (C), 142.8 (C), 135.1 (d, J=2.0 Hz, CH), 131.0 (CH), 130.2 (q, J=31.3 Hz, C), 129.0 (CH), 128.5 (CH), 126.7 (CH), 125.9 (q, J=5.4 Hz, CH), 123.0 (q, J=273.6 Hz, C), 118.9 (q, J=2.0 Hz, C), 75.4 (CH); MS (ESI) m/z: 313.0, 315.0 [M-OH, 79Br, 81Br]+; 348.0, 350.0 [M+NH4, 79Br, 81Br]+; 680.0 [2M+NH4, 79Br, 81Br]+.

Workup

  1. stirringThe mixture was stirred for 4 h at −75° C.
  2. customThe layers were separated
  3. extractionThe aqueous layer was extracted with DCM (3×10 mL)
  4. washThe combined organics were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customsolvents were removed in vacuo
  8. customThe crude residue was purified by silica gel flash chromatography (cyclohexane/AcOEt 93:7 to 90:10)

Sources & evidence

ORD record
ord-7359f5da692d4aed859fe94fdb4ed21b
Source dataset
uspto-grants-2016_08
Patent number
US09428500B2

Reaction notes

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