3-Methylbenzaldehyde → HCID 72326546, compound

HRID 1176973Notes

Reaction equation

HRID 1176973 reaction equation
[C:1]1([CH:7]2[S:12][CH2:11][CH2:10][CH2:9][S:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li]CCCC.[C:18]1([CH3:26])[CH:23]=[CH:22][CH:21]=[C:20]([CH:24]=[O:25])[CH:19]=1>C1COCC1>[C:1]1([C:7]2([CH:24]([C:20]3[CH:19]=[C:18]([CH3:26])[CH:23]=[CH:22][CH:21]=3)[OH:25])[S:8][CH2:9][CH2:10][CH2:11][S:12]2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 121053-MethylbenzaldehydeHCID 215472-Phenyl-1,3-dithianeHCID 178418339Butyllithium

Product 1

HCID 72326546HCID 72326546, compoundYield 76.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

2-Phenyl-[1,3]dithiane (JYC-II-051-A) (10.0 g, 50.9 mmol) in 100 mL of anhydrous THF w a s cooled down to −78° C. nBuLi (22.4 mL of 2.5 M solution in hexanes, 56 mmol) was added dropwise and the mixture was stirred at −78° C. for 1 h. A solution of m-tolualdehyde (6.12 g, 50.9 mmol) in anhydrous THF was added to the mixture dropwise via a cannula at −78° C. under N2 counterflow. The reaction was then warmed up to room temperature and stirred at room temperature overnight. The mixture was quenched with a saturated NH4Cl aqueous solution. The organic phase was washed with H2O and dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give brown oil. The product was purified by column chromatography (silica gel, hexanes:dichloromethane=1:2 (v/v)) to give light yellow oil (12.35 g, 76.6%). 1H NMR (300 MHz, CDCl3, δ): 7.66-7.70 (m, 2H), 7.25-7.33 (m, 3H), 6.98-7.02 (m, 2H), 6.64-6.68 (m, 1H), 6.56 (s, 1H), 4.94 (s, 1H), 2.86 (br s, 1H), 2.58-2.76 (m, 4H), 2.16 (s, 3H), 1.86-1.95 (m, 2H). 13C{1H} NMR (75 MHz, CDCl3, δ): 136.90, 136.74, 135.67, 130.14, 128.43, 128.06, 127.41, 126.86, 126.20, 124.80, 80.39, 65.90, 26.85, 26.62, 24.42, 21.04. HRMS-EI (m/z): [M]+ calcd for C18H20OS2, 316.09556; found, 316.09640.

Workup

  1. additionwas added dropwise
  2. temperatureThe reaction was then warmed up to room temperature
  3. stirringstirred at room temperature overnight
  4. customThe mixture was quenched with a saturated NH4Cl aqueous solution
  5. washThe organic phase was washed with H2O
  6. dry with materialdried over anhydrous MgSO4
  7. customThe solvent was removed under reduced pressure
  8. customto give brown oil
  9. customThe product was purified by column chromatography (silica gel, hexanes:dichloromethane=1:2 (v/v))

Sources & evidence

ORD record
ord-fb79db2ac84e40d09a02d57be48f475d
Source dataset
uspto-grants-2010_11
Patent number
US07842830B2

Reaction notes

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