Diphenylacetonitrile → Ammonia

HRID 2387664Notes

Reaction equation

HRID 2387664 reaction equation
CC(C)([O-])C.[K+].[CH3:7][C:8]1([CH3:23])[CH2:13][CH2:12]OS(=O)(=O)[N:9]1C(OC(C)(C)C)=O.[C:24]1([CH:30]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C:31]#[N:32])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>CN(C)C=O>[NH3:9].[NH2:9][C:8]([CH3:7])([CH3:23])[CH2:13][CH2:12][C:30]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:31]#[N:32]

Participants

6

Reactant 3

HCID 6837DiphenylacetonitrileHCID 23665647Potassium tert-butoxideHCID 59383129HCID 59383129, compound

Product 2

HCID 222AmmoniaHCID 54757654HCID 54757654, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Potassium tert-butoxide (203 mg, 1.81 mmol) and tert-butyl 4,4-dimethyl-1,2,3-oxathiazinane-3-carboxylate 2,2-dioxide [(400 mg, 1.51 mmol), WO2003037327, p 83] were added to a solution of diphenylacetonitrile (349 mg, 1.81 mmol) in N,N-dimethylformamide (5 mL) and the mixture was stirred for 18 hours at room temperature. The reaction mixture was then concentrated in vacuo and the residue was treated with hydrochloric acid (4M in dioxane, 10 mL) and heated at 40° C. for 2.5 hours. The reaction mixture was concentrated in vacuo and the residue was basified with saturated sodium hydrogen carbonate solution and extracted with ethyl acetate (2×30 mL). The combined organic solution was dried over magnesium sulfate, concentrated in vacuo and the residue was purified by column chromatography on silica gel, eluting with dichloromethane:methanol:0.88 ammonia, 90:10:1, to afford the title compound as a colourless oil in 77% yield, 324 mg.

Workup

  1. concentrationThe reaction mixture was then concentrated in vacuo
  2. additionthe residue was treated with hydrochloric acid (4M in dioxane, 10 mL)
  3. temperatureheated at 40° C. for 2.5 hours
  4. concentrationThe reaction mixture was concentrated in vacuo
  5. extractionextracted with ethyl acetate (2×30 mL)
  6. dry with materialThe combined organic solution was dried over magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customthe residue was purified by column chromatography on silica gel
  9. washeluting with dichloromethane

Sources & evidence

ORD record
ord-d1d4545b1d1647df9531179a6efa05e3
Source dataset
uspto-grants-2012_09
Patent number
US08268881B2

Reaction notes

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