Ammonium Chloride → HCID 18431023, compound

HRID 1278576Notes

Reaction equation

HRID 1278576 reaction equation
[NH4+:1].[Cl-].C[Al](C)C.[CH2:7]([C:10]([C:16]1[CH:21]=[CH:20][CH:19]=[C:18]([O:22][CH3:23])[CH:17]=1)([CH2:13][CH:14]=[CH2:15])[C:11]#[N:12])[CH:8]=[CH2:9]>C1(C)C=CC=CC=1.C(Cl)(Cl)Cl>[CH2:7]([C:10]([C:16]1[CH:21]=[CH:20][CH:19]=[C:18]([O:22][CH3:23])[CH:17]=1)([CH2:13][CH:14]=[CH2:15])[C:11]([NH2:1])=[NH:12])[CH:8]=[CH2:9]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 16682925TrimethylaluminumHCID 18431040HCID 18431040, compound

Product 1

HCID 18431023HCID 18431023, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 6212ChloroformSolvent

Procedure

To a suspension of NH4Cl (13.5 9, 251 mmol) in 170 mL toluene at 0° C. was added a 2.0 M solution of AlMe3 (126 mL, 251 mmol) dropwise. The mixture was warmed to room temperature and stirred for 4 hours. 2-Allyl-2-(3-methoxy-phenyl)-pent-4-enenitrile (38.1 g, 167 mmol) in 30 mL toluene was added and the mixture was heated to 80° C. for 48 hours. The mixture was cooled to room temperature and poured into a stirring suspension of silica gel (50 g) in 150 mL chloroform (CHCl3). After stirring for 30 minutes, the suspension was filtered and the silica gel was washed with methanol (MeOH). The remaining solution was concentrated to an oil and 80 mL acetone was added. The resulting suspension was filtered, the solution was concentrated and the resulting residue was dissolved in 1N hydrochloric acid (HCl)/MeOH (200 mL). The solution was concentrated, 200 mL ethyl ether (Et2O) was added and the resulting precipitate was removed by filtration and dried yielding 22.4 9 (49% yield) of the desired product. 1HNMR (400 MHz, CD3OD) δ 8.73, 8.58 (2 brs, 3H, NH), 7.34 (t, 1H), 6.93-6.91 (comp, 2H), 6.90-6.83 (comp, 1H), 5.56-5.44 (comp, 2H), 5.18-5.14 (comp, 4H), 3.79 (s, 3H), 2.82-2.79 (comp, 4H); MS (M+1) 245.3.

Workup

  1. temperaturethe mixture was heated to 80° C. for 48 hours
  2. temperatureThe mixture was cooled to room temperature
  3. stirringAfter stirring for 30 minutes
  4. filtrationthe suspension was filtered
  5. washthe silica gel was washed with methanol (MeOH)
  6. concentrationThe remaining solution was concentrated to an oil and 80 mL acetone
  7. additionwas added
  8. filtrationThe resulting suspension was filtered
  9. concentrationthe solution was concentrated
  10. dissolutionthe resulting residue was dissolved in 1N hydrochloric acid (HCl)/MeOH (200 mL)
  11. concentrationThe solution was concentrated
  12. addition200 mL ethyl ether (Et2O) was added
  13. customthe resulting precipitate was removed by filtration
  14. customdried

Sources & evidence

ORD record
ord-3980d4b09092426da01e5df4a33f518a
Source dataset
uspto-grants-2002_09
Patent number
US06444679B1

Reaction notes

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