4-Iodobenzaldehyde → HCID 72326541, compound

HRID 1176970Notes

Reaction equation

HRID 1176970 reaction equation
[CH2:1]([O:13][C:14]1[CH:15]=[C:16]([CH:33]2[S:38][CH2:37][CH2:36][CH2:35][S:34]2)[CH:17]=[CH:18][C:19]=1[O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[Li]CCCC.[I:44][C:45]1[CH:52]=[CH:51][C:48]([CH:49]=[O:50])=[CH:47][CH:46]=1>C1COCC1>[CH2:1]([O:13][C:14]1[CH:15]=[C:16]([C:33]2([CH:49]([C:48]3[CH:51]=[CH:52][C:45]([I:44])=[CH:46][CH:47]=3)[OH:50])[S:34][CH2:35][CH2:36][CH2:37][S:38]2)[CH:17]=[CH:18][C:19]=1[O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

Participants

5

Reactant 3

HCID 966574-IodobenzaldehydeHCID 59560834HCID 59560834, compoundHCID 178418339Butyllithium

Product 1

HCID 72326541HCID 72326541, compoundYield 65.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 2-(3,4-bis-dodecyloxy-phenyl)-[1,3]dithiane (12.0 g, 21.1 mmol) in 120 mL of dry THF in a Schlenk tube was cooled down to −78° C. Under N2 atmosphere, n-BuLi (9.4 mL of 2.5 M solution in hexanes, 23.4 mmol) was added dropwise to the mixture. After stirring at 0° C. for 1 h, the reaction mixture was cooled down to −78° C. and 4-iodobenzaldehyde (3.72 g, 16.0 mmol) in 100 mL of dry THF was added dropwise. The resulting mixture was allowed to warm up to room temperature and stirred at room temperature overnight. The reaction was quenched with H2O and THF was removed under reduced pressure. The resulting slurry was extracted with CH2Cl2 and the organic layer was washed with H2O and dried over anhydrous MgSO4. The solvent was removed under reduced pressure. The product was purified by column chromatography (silica gel, hexanes:dichloromethane=3:2, 1:1, then 2:3 (v/v)) to give light yellow oil (8.3 g, 65%). 1H NMR (300 MHz, CDCl3, δ): 7.44 (d, J=8.2 Hz, 2H), 7.23 (dd, J=8.5 Hz, 2.5 Hz, 1H), 7.02 (d, J=2.5 Hz, 1H), 6.78 (d, J=8.5 Hz, 1H), 6.61 (d, J=8.5 Hz, 2H), 4.84 (s, 1H), 3.98 (t, J=6.6 Hz, 2H), 3.73 (m, 2H), 3.00 (s, 1H), 2.69 (m, 4H), 1.66-1.94 (m, 6H), 1.20-1.51 (m, 36H), 0.86 (t, J=6.7 Hz, 6H). 13C{1H} NMR (75 MHz, CDCl3, δ): 148.40, 148.31, 136.96, 135.88, 130.04, 128.93, 122.95, 115.99, 112.55, 93.82, 80.51, 69.29, 69.05, 66.33, 32.00, 29.78, 29.72, 29.55, 29.45, 29.32, 29.29, 27.41, 27.02, 26.12, 24.80, 22.78, 14.24. LRMS-EI (m/z): [M−H2O]+ calcd for C41H63IO2S2, 778.3; found, 778.5.

Workup

  1. temperaturethe reaction mixture was cooled down to −78° C.
  2. temperatureto warm up to room temperature
  3. stirringstirred at room temperature overnight
  4. customThe reaction was quenched with H2O and THF
  5. customwas removed under reduced pressure
  6. extractionThe resulting slurry was extracted with CH2Cl2
  7. washthe organic layer was washed with H2O
  8. dry with materialdried over anhydrous MgSO4
  9. customThe solvent was removed under reduced pressure
  10. customThe product was purified by column chromatography (silica gel, hexanes

Sources & evidence

ORD record
ord-c57528c267bf4b08b0a50e5d836c7f59
Source dataset
uspto-grants-2010_11
Patent number
US07842830B2

Reaction notes

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