1-Butanol → 1,7-Dimethyl 4-cyano-4-(3,4-dichlorophenyl)heptanedioate

HRID 333289Notes

Reaction equation

HRID 333289 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][C:10]#[N:11])[CH:5]=[CH:6][C:7]=1[Cl:8].[CH3:12][O:13][C:14](=[O:17])[CH:15]=[CH2:16].[CH2:18](O)CCC.C[CH2:24][O:25][C:26]([CH3:28])=[O:27].CCCCCCC>CO.[OH-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:10]([C:9]([C:4]1[CH:5]=[CH:6][C:7]([Cl:8])=[C:2]([Cl:1])[CH:3]=1)([CH2:18][CH2:28][C:26]([O:25][CH3:24])=[O:27])[CH2:16][CH2:15][C:14]([O:13][CH3:12])=[O:17])#[N:11]

Participants

7

Reactant 4

HCID 2631-ButanolHCID 7294Methyl AcrylateHCID 76690(3,4-Dichlorophenyl)acetonitrileHCID 21899848Ethylacetate heptane

Product 1

HCID 108612531,7-Dimethyl 4-cyano-4-(3,4-dichlorophenyl)heptanedioate

Reagents, catalysts & solvents 2

HCID 2723671Tetrabutylammonium HydroxideCatalystHCID 887MethanolSolvent

Conditions

Temperature
70 °C

Procedure

To a 2-L, three-neck flask equipped with a temperature probe, reflux condenser, addition funnel and overhead stirrer was charged with 3,4-dichlorophenylacetonitrile (100 g, 0.54 mol), methylacrylate (139.56 g, 1.62 mol) and tent-butanol (475 mL). To the mixture was added very slowly (highly exothermic) 1.0 M solution of tetrabutylammonium hydroxide (11 mL, 0.011 mol) in methanol. After the addition was complete, the temperature rose from 21.1° C. to 68.4° C. The resulting clear solution was stirred at 70° C. for 2 h and assayed by TLC (3:7 EtOAc/Heptane; stained using Hanessian solution) and GC. The reaction mixture was cooled to room temperature before being concentrated under reduced pressure. The residue was partitioned between 2 M HCl (500 mL), brine (200 mL) and MTBE (1.5 L). The phases were separated and the aqueous phase was extracted with MTBE (250 mL). The combined organic phases were washed with brine (500 mL), dried over MgSO4 and filtered. The filtrate was concentrated under reduced pressure at 40-45° C. to yield the title compound [192.1 g, 99%, 100% (AUC) by GC] as an off-white solid. 1H NMR (DMSO-d6, 300 MHz): δ 7.75 (m, 2H), 7.45 (dd, 1H), 3.5 (s, 6H), 2.4-2.2 (m, 6H), 2.15-1.98 (m, 2H).

Workup

  1. temperaturereflux
  2. additioncondenser, addition funnel and overhead stirrer
  3. additionAfter the addition
  4. customrose from 21.1° C. to 68.4° C
  5. temperatureThe reaction mixture was cooled to room temperature
  6. concentrationbefore being concentrated under reduced pressure
  7. customThe residue was partitioned between 2 M HCl (500 mL), brine (200 mL) and MTBE (1.5 L)
  8. customThe phases were separated
  9. extractionthe aqueous phase was extracted with MTBE (250 mL)
  10. washThe combined organic phases were washed with brine (500 mL)
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. concentrationThe filtrate was concentrated under reduced pressure at 40-45° C.

Sources & evidence

ORD record
ord-0e6ddf9ed7a24a3896d66183b83c974d
Source dataset
uspto-grants-2014_11
Patent number
US08877975B2

Reaction notes

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