Phenylacetonitrile → HCID 178510757, compound

HRID 2307803Notes

Reaction equation

HRID 2307803 reaction equation
F[C:2]1[N:7]=[C:6]2[NH:8][N:9]=[C:10]([C:11]3[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=3)[C:5]2=[CH:4][CH:3]=1.[CH2:17]([C:24]#[N:25])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.[H-].[Na+].[NH4+].[Cl-]>CN(C=O)C.CO.CCOC(C)=O>[C:18]1([CH:17]([C:2]2[N:7]=[C:6]3[NH:8][N:9]=[C:10]([C:11]4[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=4)[C:5]3=[CH:4][CH:3]=2)[C:24]#[N:25])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

7

Reactant 4

HCID 8794PhenylacetonitrileHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 178505427HCID 178505427, compound

Product 1

HCID 178510757HCID 178510757, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 21584119Ethylacetate methanolSolvent

Conditions

Temperature
-20 °C

Procedure

To a stirred mixture of Example 227C (0.96 g, 4.48 mmol) in DMF (20 mL) at −35° C. was added benzyl cyanide (1.55 mL, 13.4 mmol) and then NaH (0.57 g of 95% NaH, 22.4 mmol). The resulting dark red mixture was stirred 15 min while being slowly warmed to ˜−20° C. At this time most of the bubbling had stopped and the reaction mixture was then quickly warmed to room temperature and then to 100° C. overnight. The reaction mixture was cooled to room temperature and saturated aqueous NH4Cl was added. The mixture was extracted with EtOAc and the organic extracts washed twice with H2O and once with brine. Silica gel was added and the volatiles removed on a rotary evaporator. Flash chromatography (60-80-100% EtOAc-3% MeOH/EtOAc) gave 1.14 g (82%) of as an orange solid. Rf=0.40 (5% MeOH/EtOAc); MS m/z 312 (M+H)+; 1H NMR (300 MHz, DMSO-D6) δ ppm 6.17 (s, 1 H) 7.40 (m, 4 H) 7.52 (m, 2 H) 8.00 (m, 2 H) 8.70 (m, 2 H) 8.74 (d, J=8.48 Hz, 1 H) 14.36 (s, 1 H); Anal Calcd for C19H13N5: C, 73.30; H, 4.21; N, 22.49. Found: C, 73.09; H, 4.10; N, 22.58.

Workup

  1. temperaturethe reaction mixture was then quickly warmed to room temperature
  2. customto 100° C.
  3. customovernight
  4. temperatureThe reaction mixture was cooled to room temperature
  5. extractionThe mixture was extracted with EtOAc
  6. washthe organic extracts washed twice with H2O and once with brine
  7. additionSilica gel was added
  8. customthe volatiles removed on a rotary evaporator
  9. customFlash chromatography (60-80-100% EtOAc-3% MeOH/EtOAc) gave 1.14 g (82%) of as an orange solid

Sources & evidence

ORD record
ord-da97809b7fc64a83bef3239e381765a5
Source dataset
uspto-grants-2004_12
Patent number
US06831175B2

Reaction notes

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