Dimethyl Carbonate → HCID 59161726, compound

HRID 2427866Notes

Reaction equation

HRID 2427866 reaction equation
[Li+].CC([N-]C(C)C)C.[CH3:9][C:10]1[CH:15]=[C:14]([C:16]2[CH:21]=[CH:20][C:19]([C:22]([F:25])([F:24])[F:23])=[CH:18][CH:17]=2)[N:13]=[C:12]([C:26]2[CH:31]=[CH:30][C:29]([C:32]([F:35])([F:34])[F:33])=[CH:28][CH:27]=2)[CH:11]=1.[C:36](=O)([O:39]C)[O:37][CH3:38]>>[CH3:38][O:37][C:36](=[O:39])[CH2:9][C:10]1[CH:15]=[C:14]([C:16]2[CH:21]=[CH:20][C:19]([C:22]([F:25])([F:24])[F:23])=[CH:18][CH:17]=2)[N:13]=[C:12]([C:26]2[CH:31]=[CH:30][C:29]([C:32]([F:35])([F:33])[F:34])=[CH:28][CH:27]=2)[CH:11]=1

Participants

4

Reactant 3

HCID 12021Dimethyl CarbonateHCID 2724682Lithium diisopropylamideHCID 59161722HCID 59161722, compound

Product 1

HCID 59161726HCID 59161726, compoundYield 87.3%

Conditions

Temperature
-78 °C

Procedure

A solution of LDA (1.8 M in THF/heptane/ethyl benzene, 4.4 mL, 7.92 mmol) was added slowly to a stirred solution of 4-methyl-2,6-bis-(4-trifluoromethylphenyl)-pyridine (1.37 g, 3.6 mmol) under N2 at −78° C. After 30 minutes, dimethyl carbonate (720 μL, 8.0 mmol) was added. After stirring at −78° C. for an additional 30 minutes, the solution was allowed to warm up slowly and stirred at 0° C. for 30 minutes The reaction was quenched with saturated aqueous NH4Cl (10 mL). The mixture was partitioned between CH2Cl2 and H2O. The aqueous layer was extracted with CH2Cl2 (2×). The combined extracts were washed with brine, then dried (Na2SO4), filtered and evaporated. The residue was purified by column chromatography on silica gel (10-50% CH2Cl2 in heptane) to give the product as a white solid (1.38 g, 87%). 1H NMR (300 MHz, CDCl3) δ 8.24 (d, J=7.91 Hz, 4H), 7.76 (d, J=7.91 Hz, 4H), 7.72 (s, 2H), 3.80 (s, 2H), 3.77 (s, 3H). MS m/e 440.2 (M+H)

Workup

  1. temperatureto warm up slowly
  2. stirringstirred at 0° C. for 30 minutes The reaction
  3. customwas quenched with saturated aqueous NH4Cl (10 mL)
  4. customThe mixture was partitioned between CH2Cl2 and H2O
  5. extractionThe aqueous layer was extracted with CH2Cl2 (2×)
  6. washThe combined extracts were washed with brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by column chromatography on silica gel (10-50% CH2Cl2 in heptane)

Sources & evidence

ORD record
ord-67de6477075f451d8fd1042cb8b6dcb5
Source dataset
uspto-grants-2011_06
Patent number
US07968725B2

Reaction notes

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