1,7-Dimethyl 4-cyano-4-(3,4-dichlorophenyl)heptanedioate → HCID 12595532, compound

HRID 333290Notes

Reaction equation

HRID 333290 reaction equation
CC(C)([O-])C.[K+].[C:7]([C:9]([C:22]1[CH:27]=[CH:26][C:25]([Cl:28])=[C:24]([Cl:29])[CH:23]=1)([CH2:16][CH2:17][C:18]([O:20]C)=O)[CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13])#[N:8].CCOC(C)=O.CCCCCCC>C1(C)C=CC=CC=1>[C:7]([C:9]1([C:22]2[CH:27]=[CH:26][C:25]([Cl:28])=[C:24]([Cl:29])[CH:23]=2)[CH2:10][CH:11]([C:12]([O:14][CH3:15])=[O:13])[C:18](=[O:20])[CH2:17][CH2:16]1)#[N:8]

Participants

5

Reactant 3

HCID 108612531,7-Dimethyl 4-cyano-4-(3,4-dichlorophenyl)heptanedioateHCID 21899848Ethylacetate heptaneHCID 23665647Potassium tert-butoxide

Product 1

HCID 12595532HCID 12595532, compoundYield 121.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
90 °C

Procedure

To a 12-L, three-neck flask equipped with a temperature probe, reflux condenser, addition funnel and overhead stirrer was charged with potassium tert-butoxide (266 g, 2.3 mol) and toluene (1 L). A solution of dimethyl 4-cyano-4-(3,4-dichlorophenyl)-heptanedioate (402 g, crude, 386 g theoretical, 1.07 mol) in toluene (3 L) was added through an addition funnel. The reaction mixture was heated to 90° C. and stirred for 1 h. The progress of the reaction was monitored by TLC (4:6 EtOAc/Heptane; stained using Hanessian solution). After 1 h, the reaction mixture was cooled to 15° C. and quenched slowly with 2 M HCl (2.3 L). The phases were separated and the aqueous phase was extracted with MTBE (1 L). The combined organic phases were washed with brine (2×1 L), dried over MgSO4, filtered and concentrated under reduced pressure at 40-45° C. to yield the title compound (424 g, >100%) as a yellow solid. The crude was taken into next step without further purification.

Workup

  1. temperaturereflux
  2. additioncondenser, addition funnel and overhead stirrer
  3. waitAfter 1 h
  4. temperaturethe reaction mixture was cooled to 15° C.
  5. customquenched slowly with 2 M HCl (2.3 L)
  6. customThe phases were separated
  7. extractionthe aqueous phase was extracted with MTBE (1 L)
  8. washThe combined organic phases were washed with brine (2×1 L)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure at 40-45° C.

Sources & evidence

ORD record
ord-b9040b7859144b2197d8d2d9e277e653
Source dataset
uspto-grants-2014_11
Patent number
US08877975B2

Reaction notes

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