Diethyl Oxalate → HCID 13560089, compound

HRID 66597Notes

Reaction equation

HRID 66597 reaction equation
Br[C:2]1[CH:3]=[C:4]([Cl:12])[CH:5]=[C:6]2[C:11]=1[N:10]=[CH:9][CH:8]=[CH:7]2.C([Li])CCC.[C:18](OCC)(=[O:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20]>O1CCCC1>[Cl:12][C:4]1[CH:5]=[C:6]2[C:11](=[C:2]([C:18](=[O:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH:3]=1)[N:10]=[CH:9][CH:8]=[CH:7]2

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 218182138-Bromo-6-chloroquinolineHCID 178418339Butyllithium

Product 1

HCID 13560089HCID 13560089, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

8-Bromo-6-chloroquinoline [J. Het. Chem. 6, pp. 243-245 (1969); 6 g., 0.025 mole] in 50 ml. of tetrahydrofuran was added dropwise over a 10 minute period to a mixture of butyl lithium (2.3 M in hexane, 12.2 ml., 0.028 mole) and 40 ml. of tetrahydrofuran held at -70° C. After an additional 30 minutes at this temperature, a cold (0° C.) solution of diethyl oxalate (14.6 g., 0.10 mole) in 50 ml. of tetrahydrofuran was added dropwise. The reaction mixture was maintained at 0° C. for 1 hour, then quenched at 0°-5° C. with glacial acetic acid (17 ml.) in 50 ml. of tetrahydrofuran. After warming to room temperature the quenched mixture was poured into 500 ml. of water and then diluted with 500 ml. of ethyl acetate and 500 ml. of saturated sodium bicarbonate. The organic layer was separated, washed with 500 ml. of fresh bicarbonate, dried over anhydrous magnesium sulfate, filtered, and evaporated to an oil. Trituration with two 100 ml. portions of hexane gave the title product (2.3 g., m.p. 107°-110° C.; m/e 265/263).

Workup

  1. customheld at -70° C
  2. customquenched at 0°-5° C. with glacial acetic acid (17 ml.) in 50 ml
  3. temperatureAfter warming to room temperature the quenched mixture
  4. additionwas poured into 500 ml
  5. additionof water and then diluted with 500 ml
  6. customThe organic layer was separated
  7. washwashed with 500 ml
  8. dry with materialof fresh bicarbonate, dried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. customevaporated to an oil

Sources & evidence

ORD record
ord-718b23cf93ce4c52a4da93d9244cf297
Source dataset
uspto-grants-1982_08
Patent number
US04342771

Reaction notes

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