Bromoacetonitrile → Ethyl 2,2-bis(4-chlorophenyl)-3-cyanopropanoate

HRID 2408850Notes

Reaction equation

HRID 2408850 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=2)[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:4][CH:3]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].Br[CH2:32][C:33]#[N:34]>O1CCCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([C:14]2[CH:15]=[CH:16][C:17]([Cl:20])=[CH:18][CH:19]=2)([CH2:32][C:33]#[N:34])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 11534BromoacetonitrileHCID 101291Benzeneacetic acid, 4-chloro-alpha-(4-chlorophenyl)-, ethyl esterHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 67387582Ethyl 2,2-bis(4-chlorophenyl)-3-cyanopropanoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Ethyl 2,2-bis(4-chlorophenyl)acetate (5.50 g, 17.8 mmol) was dissolved in 100 mL of dry tetrahydrofuran and cooled to −78° C. Lithium bis(trimethylsilyl)amide (1.0 M in hexane, 18.0 mL, 18.0 mmol) was added dropwise via syringe under nitrogen. The reaction was brought to 0° C., stirred for 1 hour, and then cooled to −78° C. A solution of bromoacetonitrile (1.24 mL, 17.8 mmol) dissolved in tetrahydrofuran was added, and the reaction was stirred for 2 hours while warming to room temperature. The reaction was quenched with saturated NH4Cl solution and extracted with diethyl ether. The organic phase was washed with brine, dried over MgSO4, filtered, and concentrated. Chromatography on silica gel (Analogix Intelliflash 280; 10% ethyl acetate/hexane) yielded the title compound: 1H NMR (300 MHz, CDCl3) δ ppm 7.38-7.32 (m, 4H), 7.22-7.17 (m, 4H), 4.25 (q, J=7.2, 2H), 3.32 (s, 2H), 1.23 (t, J=7.2, 3H); MS (DCI+) m/z 365 (M+NH4)+.

Workup

  1. customwas brought to 0° C.
  2. temperaturecooled to −78° C
  3. additionwas added
  4. stirringthe reaction was stirred for 2 hours
  5. temperaturewhile warming to room temperature
  6. customThe reaction was quenched with saturated NH4Cl solution
  7. extractionextracted with diethyl ether
  8. washThe organic phase was washed with brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-8ff1763dee7448c89d898807d294e7ea
Source dataset
uspto-grants-2014_08
Patent number
US08815869B2

Reaction notes

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