Ethyl Acetate → HCID 14892331, compound

HRID 1919696Notes

Reaction equation

HRID 1919696 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]([C:8]([O:10][C:11]2[CH:16]=CC=C[CH:12]=2)=[O:9])[CH:4]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[CH:3]=1.[CH3:28]C(C)([O-])C.[K+].CCOC(C)=O>C1COCC1>[C:11]([O:10][C:8]([N:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]1[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])=[O:9])([CH3:12])([CH3:16])[CH3:28]

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 14892326HCID 14892326, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 14892331HCID 14892331, compoundYield 83%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-42 °C

Procedure

To a stirred solution of the 4-Chloro-1-(phenoxycarbonyl)-2-n-undecyl-1,2-dihydropyridine (5.31 g, 13.62 mmol) in 157 ml of THF at −42° C. was added dropwise over 15 minutes a 11.0M solution of potassium t-butoxide (54.5 ml, 54.5 mmol). The resulting orange solution was stirred for 1 h at −42° C. The cooling bath was removed, and the reaction mixture was allowed to stir for 20 min while being slowly warmed to room temperature. Water (40 ml) and ether (80 ml) were added and the aqueous phase was extracted twice with ether. The combined organic extracts were washed with cold 1.0 N NaOH (2×35 ml), and brine. The organic phase was dried over MgSO4, filtered through Celite, and concentrated by evaporation to give the crude product. Column chromatography with 5% EtOAc in hexanes afforded 3.5 g (83%) of the product as a colorless oil which was homogeneous by TLC analysis. 1H NMR (300 MHz) d 6.92-6.61 (pair of br d, 1H), 5.53 (pair of br d, 1H), 5.55 (br s, 1H), 5.25-5.11 (pair of br d, 1H), 4.82-4.63 (br m, 1H), 1.53 (s, 9H), 1.24 (br s, 20H), 0.83 (t, 3H); 13C NMR (75 MHz) 152.6 (s), 151.8 (s), 127.7 (s), 127.5 (s), 117.8 (s), 117.4 (s), 106.6 (s), 106.2 (s), 81.7 (s), 54.1 (s), 53.2 (s), 34.3 (s), 33.8 (s), 31.9 (s), 29.7 (s), 29.6 (s), 29.5 (s), 29.3 (s), 28.1 (s), 24.3 (s), 22.7 (s), 14.1 (s) ppm; FT-IR 2954, 2926, 2855, 1717, 1633, 1369, 1390, 1171, 1145, 1129, 1054 cm−1.

Workup

  1. customThe cooling bath was removed
  2. stirringto stir for 20 min
  3. temperaturewhile being slowly warmed to room temperature
  4. additionWater (40 ml) and ether (80 ml) were added
  5. extractionthe aqueous phase was extracted twice with ether
  6. washThe combined organic extracts were washed with cold 1.0 N NaOH (2×35 ml), and brine
  7. dry with materialThe organic phase was dried over MgSO4
  8. filtrationfiltered through Celite
  9. concentrationconcentrated by evaporation
  10. customto give the crude product

Sources & evidence

ORD record
ord-3aee5c1e01c54390aa22055c73452f7a
Source dataset
uspto-grants-2012_05
Patent number
US08168657B2

Reaction notes

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