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

HRID 2408850ノート

反応式

HRID 2408850 の反応式
[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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

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)+.

後処理

  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

出典と根拠

ORDレコード
ord-8ff1763dee7448c89d898807d294e7ea
出典データセット
uspto-grants-2014_08
特許番号
US08815869B2

反応ノート

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