Tetrahydrofuran → Methyl 5-cyano-5-(4-fluorophenyl)-2-oxocyclohexanecarboxylate

HRID 462277Notes

Reaction equation

HRID 462277 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:19]#[N:20])([CH2:14][CH2:15][C:16]([OH:18])=O)[CH2:9][CH2:10][C:11]([OH:13])=[O:12])=[CH:4][CH:3]=1.O1CCC[CH2:22]1.CC(C)([O-])C.[K+]>C(O)(=O)C>[C:11]([CH:10]1[CH2:9][C:8]([C:19]#[N:20])([C:5]2[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=2)[CH2:14][CH2:15][C:16]1=[O:18])([O:13][CH3:22])=[O:12]

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 20453289HCID 20453289, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 12230235Methyl 5-cyano-5-(4-fluorophenyl)-2-oxocyclohexanecarboxylateYield 93%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution consisting of 42.71 gm. (0.139 mole) of the dimethyl ester of 4-(p-fluorophenyl)-4-cyanopimelic acid (prepared in Part A, above) and 900 ml. tetrahydrofuran is added 31.3 gm. (0.28 mole) potassium tert-butoxide. This reaction mixture is heated at the reflux temperature for 4 1/2 hours. It is allowed to cool. It is then chilled in ice and 225 ml. of 2.5 N aqueous acetic acid is added. The organic layer that forms is recovered and diluted with 750 ml. benzene. The benzene:tetrahydrofuran solution is washed successively with sodium bicarbonate, with water, and finally with brine. The solvents are then removed by evaporation under reduced pressure to give 35.6 gm. (93% yield) of 2-carbomethoxy-4-cyano-4-(p-fluorophenyl)cyclohexanone as a gum.

Workup

  1. temperatureThis reaction mixture is heated at the reflux temperature for 4 1/2 hours
  2. temperatureto cool
  3. temperatureIt is then chilled in ice
  4. customThe organic layer that forms is recovered
  5. additiondiluted with 750 ml
  6. washThe benzene:tetrahydrofuran solution is washed successively with sodium bicarbonate, with water
  7. customThe solvents are then removed by evaporation under reduced pressure
  8. customto give 35.6 gm

Sources & evidence

ORD record
ord-df00506120304faa82aecdf740ddd756
Source dataset
uspto-grants-1977_12
Patent number
US04065573

Reaction notes

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