Sodium hydride → 4-{2-Cyano-2-[(diphenylmethylene)amino]ethyl}-3-fluorobenzonitrile

HRID 239855

반응식

HRID 239855 반응식
[H-].[Na+].[C:3]1([C:9](=[N:16][CH2:17][C:18]#[N:19])[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Br[CH2:21][C:22]1[CH:29]=[CH:28][C:25]([C:26]#[N:27])=[CH:24][C:23]=1[F:30]>CN(C)C=O>[C:18]([CH:17]([N:16]=[C:9]([C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)[C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1)[CH2:21][C:22]1[CH:29]=[CH:28][C:25]([C:26]#[N:27])=[CH:24][C:23]=1[F:30])#[N:19]

참가 물질

5

반응물 3

HCID 24758Sodium hydrideHCID 612957[(Diphenylmethylene)amino]acetonitrileHCID 27831494-(Bromomethyl)-3-fluorobenzonitrile

생성물 1

HCID 866481454-{2-Cyano-2-[(diphenylmethylene)amino]ethyl}-3-fluorobenzonitrile

시약·촉매·용매 1

HCID 6228Dimethylformamide용매3회

반응 조건

온도
0 °C

실험 절차

To a suspension of sodium hydride (2.62 g) in dimethylformamide (100 ml) at 0° C. was slowly added a solution of [(diphenylmethylidene)amino]acetonitrile (13.20 g) in 40 ml of dimethylformamide. The reaction temperature varied between 2 and 8° C. during the addition. The color went from yellow to brown with gas evolution. The reaction mixture was stirred at 0° C. for 10 more minutes then 4-(bromomethyl)-3-fluorobenzonitrile from step 1 (12.72 g) was added very quickly in 60 ml of dimethylformamide. The temperature rose to 27° C. and the cold bath was removed. The reaction was stirred for 4 h. The flask content was poured into sodium dihydrogen phosphate solution (300 ml) and icy water (1.4 L). The mixture turned yellow and a big lump formed along with very small amounts of fine powder. The fine solid was filtered and the lump kept in the Erlenmeyer. The lump was dissolved in ether (500 ml) and put in a separating funnel along with water (200 ml). The phases were separated and the organic layer was washed with brine (100 ml) and dried over magnesium sulfate. The organic phase is concentrated under reduced pressure to give 4-{2-cyano-2-[(diphenylmethylene)amino]ethyl}-3-fluorobenzonitrile an orange solid that was used as such in the next step.

후처리

  1. additionThe reaction temperature varied between 2 and 8° C. during the addition
  2. customrose to 27° C.
  3. customthe cold bath was removed
  4. stirringThe reaction was stirred for 4 h
  5. additionThe flask content was poured into sodium dihydrogen phosphate solution (300 ml) and icy water (1.4 L)
  6. customa big lump formed along with very small amounts of fine powder
  7. filtrationThe fine solid was filtered
  8. dissolutionThe lump was dissolved in ether (500 ml)
  9. customput in a separating funnel along with water (200 ml)
  10. customThe phases were separated
  11. washthe organic layer was washed with brine (100 ml)
  12. dry with materialdried over magnesium sulfate
  13. concentrationThe organic phase is concentrated under reduced pressure

출처 및 근거

ORD 기록
ord-20f3090f197346ebba2947d136a1ac6d
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08642799B2

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