Acetone → HCID 86709941, compound

HRID 1526775Notes

Reaction equation

HRID 1526775 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]2[O:13][CH2:12][CH2:11][O:10]2)[CH:5]=[C:6]([Cl:8])[CH:7]=1.C([Li])(C)(C)C.CCCCC.[CH3:24][C:25]([CH3:27])=[O:26]>C(OCC)C>[Cl:8][C:6]1[CH:7]=[C:2]([C:25]([OH:26])([CH3:27])[CH3:24])[CH:3]=[C:4]([CH:9]2[O:13][CH2:12][CH2:11][O:10]2)[CH:5]=1

Participants

6

Reactant 4

HCID 180AcetoneHCID 8003PentaneHCID 539351942-(3-Bromo-5-chlorophenyl)-1,3-dioxolaneHCID 178418306HCID 178418306, compound

Product 1

HCID 86709941HCID 86709941, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 2-(3-bromo-5-chlorophenyl)-1,3-dioxolane (3.34 g, 12.68 mmol) in anhydrous diethyl ether (40 mL) in a dried flask was slowly added a 1.70 M solution of tert-butyl lithium in pentane (15.0 mL, 25.50 mmol) at −78° C. under nitrogen to give a pinkish-yellow suspension. The reaction mixture was stirred at −78° C. for 45 min under nitrogen atmosphere. After 45 min, the reaction mixture was warmed to −30° C. and stirred at that temperature for 2 h. Acetone (2.0 mL, 25.35 mmol) was added drop wise to the above solution and the reaction mixture stirred at −30° C. for another 3 h. The reaction mixture was quenched with a saturated NH4Cl solution (20 mL) at −30° C. and the reaction mixture was warmed slowly to room temperature (30 min) and then diluted with diethyl ether (25.0 mL). The ether layer was separated and then washed with water (1×25 mL), dried over anhydrous Na2SO4, filtered and evaporated on the rot-yap to give a pale yellow viscous liquid (5.45 g from two runs). GC-MS analysis (EI mode) of the product shows the desired product's mass: m/z 241 (35ClM+) and m/z 243 (37ClM+), Calcd for C12H15BrClO3: 242.67. LC-MS analysis of the crude product shows the desired product's mass: m/z 243 (35ClM+H), m/z 245 (37ClM+H), m/z 225 (35ClM+H−H2O), m/z 227 (37ClM+H−H2O). 1H NMR (400 MHz, CDCl3): δ 1.54 (s, 6H, (CH3)2C—OH), 3.90-4.25 (M, 4H, 2×—CH2—O—), 5.75 (s, 1H, O—CH-0), 7.34 (s, 1H), 7.43 (d, 2H). 1H NMR spectrum of the sample was consistent with the suggested structure of the product.

Workup

  1. customto give a pinkish-yellow suspension
  2. waitAfter 45 min
  3. temperaturethe reaction mixture was warmed to −30° C.
  4. stirringstirred at that temperature for 2 h
  5. stirringthe reaction mixture stirred at −30° C. for another 3 h
  6. customThe reaction mixture was quenched with a saturated NH4Cl solution (20 mL) at −30° C.
  7. temperaturethe reaction mixture was warmed slowly to room temperature (30 min)
  8. additiondiluted with diethyl ether (25.0 mL)
  9. customThe ether layer was separated
  10. washwashed with water (1×25 mL)
  11. dry with materialdried over anhydrous Na2SO4
  12. filtrationfiltered
  13. customevaporated on the rot-yap
  14. customto give a pale yellow viscous liquid (5.45 g from two runs)

Sources & evidence

ORD record
ord-47289b309e794efc89f05b81dd177d8b
Source dataset
uspto-grants-2015_07
Patent number
US09085606B2

Reaction notes

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