Benzene → Serinol Bisphthalonitrile

HRID 39204

Reaction equation

HRID 39204 reaction equation
[NH2:1][CH:2]([CH2:5][OH:6])[CH2:3][OH:4].[N+]([C:10]1[CH:17]=[CH:16][CH:15]=[C:12]([C:13]#[N:14])[C:11]=1[C:18]#[N:19])([O-])=O.C([O-])([O-])=O.[K+].[K+].C1C=CC=CC=1>CS(C)=O.CC#N>[C:18](#[N:19])[C:11]1[C:12](=[CH:15][CH:16]=[CH:17][CH:10]=1)[C:13]#[N:14].[C:18](#[N:19])[C:11]1[C:12](=[CH:15][CH:16]=[CH:17][CH:10]=1)[C:13]#[N:14].[NH2:1][CH:2]([CH2:5][OH:6])[CH2:3][OH:4]

Participants

7

Reactant 4

HCID 241BenzeneHCID 11430Potassium CarbonateHCID 68294SerinolHCID 1626521,2-Benzenedicarbonitrile, 3-nitro-2×

Product 1

HCID 86633587Serinol Bisphthalonitrile

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6342AcetonitrileSolvent

Procedure

A mixture of serinol (45.8 mg, 0.50 mmol, 1 equiv.), 3-nitrophthalonitrile (258.1 mg, 1.5 mmol, 2.5 equiv.) and K2CO3 (277.4 mg, 2.0 mmol, 4 equiv.) in 3 mL DMSO was stirred at room temperature and monitored periodically by TLC (9:1 benzene:CH3CN). The reaction mixture changed from orange to brown as the reaction occurred. After 90 h, the reaction mixture was heated to 70° C. TLC analysis showed the gradual disappearance of 3-nitrophthalonitrile over the next 8.5 h. The reaction mixture was partitioned between EtOAc and water, and the two layers were separated. The aqueous layer was extracted with EtOAc. This organic extract was combined with the phase-separated organic layer from the original separation, and then this mixture was washed twice with saturated NaHCO3, twice with water, and once with saturated NaCl. TLC analysis of the crude material showed no ninhydrin positive spot. The crude material was purified by flash chromatography using benzene:CH3CN (95:5) to extract the major UV-active spot.

Workup

  1. temperaturethe reaction mixture was heated to 70° C
  2. customover the next 8.5 h
  3. customThe reaction mixture was partitioned between EtOAc and water
  4. customthe two layers were separated
  5. extractionThe aqueous layer was extracted with EtOAc
  6. extractionThis organic extract
  7. customwas combined with the phase-separated organic layer from the original separation
  8. washthis mixture was washed twice with saturated NaHCO3, twice with water
  9. customThe crude material was purified by flash chromatography
  10. extractionto extract the major UV-active spot

Sources & evidence

ORD record
ord-f97695d5d8364f23a12a894e5a9b6c7f
Source dataset
uspto-grants-2013_09
Patent number
US08524891B2

Linked notes

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