(3,4-Dichlorophenyl)acetonitrile → HCID 59683693, compound

HRID 1096745Notes

Reaction equation

HRID 1096745 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].[CH2:12]1[O:14][C@H:13]1[CH2:15]Cl.ClCCl.CCCCCC>O1CCCC1>[Cl:1][C:2]1[CH:3]=[C:4]([C@:9]2([C:10]#[N:11])[CH2:15][CH:13]2[CH2:12][OH:14])[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

5

Reactant 3

HCID 76690(3,4-Dichlorophenyl)acetonitrileHCID 2734062(-)-EpichlorohydrinHCID 21226440Methylenechloride Hexane

Product 1

HCID 59683693HCID 59683693, compoundYield 64.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-25 °C

Procedure

3,4-Dichlorophenyl acetonitrile (40 g, 215 mmole) was dissolved in dry tetrahydrofuran (THF, 350mL) under nitrogen atmosphere, The solution was cooled to −25° C. and soda amide (8.3 g, 215 mmol) was added portion wise maintaining the temperature of the reaction mass −25° C. The reaction mixture was allowed to warm to room temperature and maintained for 2 hours. It was then cooled to −25° C. A solution of R-(−) epichlorohydrin (19.89 g, 215 mmol) in tetrahydrofuran (50 mL) was added drop wise at −25° C. followed by the portion wise addition of soda amide (8.3 g, 250 mmol). The temperature of the reaction mass was then gradually raised to room temperature over a period of 8 hours. The reaction was monitored by TLC (dichloromethane/hexane (1:1)). The reaction mass was quenched with saturated ammonium chloride solution. The aqueous layer was extracted with ethyl acetate (3×500 mL).The combined organic layer was dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to yield 58 g of crude oil. The crude oil was purified by column chromatography (silica gel, dichloromethane/hexane (9:1) to yield 33.4 g (64%) of product. 1H NMR δ(300 MHz,CDCl3): 1.59-1.67 (3H,m), 1.88-1.97 (1H,m), 3.72-3.79 (1H,m), 4.06-4.12 (1H,m), 7.13-7.17 (1H,m) 7.39-7.52 (2H,m).

Workup

  1. temperaturewise maintaining the temperature of the reaction mass −25° C
  2. temperatureto warm to room temperature
  3. temperaturemaintained for 2 hours
  4. temperatureIt was then cooled to −25° C
  5. temperatureThe temperature of the reaction mass was then gradually raised to room temperature over a period of 8 hours
  6. customThe reaction mass was quenched with saturated ammonium chloride solution
  7. extractionThe aqueous layer was extracted with ethyl acetate (3×500 mL).The combined organic layer
  8. dry with materialwas dried over anhydrous sodium sulphate
  9. filtrationfiltered
  10. customevaporated under reduced pressure
  11. customto yield 58 g of crude oil
  12. customThe crude oil was purified by column chromatography (silica gel, dichloromethane/hexane (9:1)

Sources & evidence

ORD record
ord-9e225359ae294bdda6a32b98c2ee7bcd
Source dataset
uspto-grants-2012_03
Patent number
US08138377B2

Reaction notes

Loading…