Hydrochloric Acid → HCID 118372882, compound

HRID 2282068Notes

Reaction equation

HRID 2282068 reaction equation
F[C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([F:10])[C:3]=1[C:4]#[N:5].[C:11](=[O:14])([O-])[O-].[K+].[K+].O[C:18]1[CH:25]=[CH:24][CH:23]=[C:22]([OH:26])[C:19]=1[C:20]#[N:21].Cl>CN(C)C(=O)C>[C:4]([C:3]1[C:6]([F:10])=[CH:7][CH:8]=[CH:9][C:2]=1[O:26][C:22]1[CH:23]=[CH:24][CH:25]=[C:18]([O:14][C:11]2[CH:9]=[CH:8][CH:7]=[C:6]([F:10])[C:3]=2[C:4]#[N:5])[C:19]=1[C:20]#[N:21])#[N:5]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 746952,6-DifluorobenzonitrileHCID 937912,6-Dihydroxybenzonitrile

Product 1

HCID 118372882HCID 118372882, compoundYield 639.3%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent2×

Procedure

Into a 500 mL 3-neck round bottom flask equipped with stir bar, condenser, nitrogen inlet, and addition funnel was charged, 2,6-difluorobenzonitrile (50.0 g, 35.9 mmol), potassium carbonate (29.80 g, 28.8 mmol), and N,N-dimethylacetamide (DMAc, 100 mL). A solution containing 2,6-dihydroxybenzonitrile (12.2 g, 9.00 mmol) and DMAc (75 mL) was added dropwise over 6 hours at 70° C. The mixture was stirred at 70° C. for 72 hours. The reaction mixture was then poured into 2 M HCl (600 mL), and the precipitate was collected by filtration and washed with water. After air drying, the solid was dissolved with acetone (600 mL). The mixture was stirred at room temperature for 3 hours, followed by filtration to remove insoluble impurities. The filtrate was evaporated to dryness on a rotary evaporator. The resulting solid was extracted with hot toluene to afford 21.48 g (64.0%) of a brown solid (3CN trimer; 4 in FIG. 1), m.p. 216.1-218.4° C. 1H-NMR (DMSO-d6): 7.18-7.22 (m, 4H, Ar—H), 7.41-7.45 (t, 2H, Ar—H), 7.78-7.86 (m, 3H, Ar—H). 13C-NMR (DMSO-d6): 93.61, 93.80, 97.30, 110.58, 111.48, 112.40, 112.79, 114.86, 115.40, 136.77, 136.94, 137.04, 157.41157.76, 161.88, 164.44.

Workup

  1. customInto a 500 mL 3-neck round bottom flask equipped
  2. additionbar, condenser, nitrogen inlet, and addition funnel
  3. additionwas charged
  4. additionwas added dropwise over 6 hours at 70° C
  5. stirringThe mixture was stirred at 70° C. for 72 hours
  6. filtrationthe precipitate was collected by filtration
  7. washwashed with water
  8. customAfter air drying
  9. dissolutionthe solid was dissolved with acetone (600 mL)
  10. stirringThe mixture was stirred at room temperature for 3 hours
  11. filtrationfollowed by filtration
  12. customto remove insoluble impurities
  13. customThe filtrate was evaporated to dryness on a rotary evaporator
  14. extractionThe resulting solid was extracted with hot toluene

Sources & evidence

ORD record
ord-5514c90781ba4d7b927eb958fdb13672
Source dataset
uspto-grants-2015_09
Patent number
US09139696B1

Reaction notes

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