Sulfuric Acid → HCID 18349269, compound

HRID 1584990Notes

Reaction equation

HRID 1584990 reaction equation
C(C1[O:7][C:6]2C=CC(C#N)=C[C:5]=2[CH:4]=1)#N.S(=O)(=O)(O)[OH:15].CC[O:21][CH2:22]C.[CH2:24]1[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]1>C(Cl)Cl>[CH:6]([C:5]1[O:15][C:25]2[CH:26]=[CH:27][C:28]([CH:22]=[O:21])=[CH:29][C:24]=2[CH:4]=1)=[O:7]

Participants

6

Reactant 4

HCID 1118Sulfuric Acid2×HCID 3283Diethyl EtherHCID 8078CyclohexaneHCID 18349288HCID 18349288, compound

Product 1

HCID 18349269HCID 18349269, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Diisobutylaluminum halide (4.26 g, 0.03 mole; 30 mL of a 1M solution in cyclohexane) is added dropwise to a solution of 2,5-dicyanobenzo[b]furan (1.68g, 0.01 mole) in 150 mL dry methylenechloride at 15° C., under nitrogen. The mixture is stirred for 15 minutes and then allowed to reflux for 40 minutes. The reaction mixture is cooled and 100 mL 1M sulfuric acid is added slowly while keeping the temperature below 25° C. After addition of the sulfuric acid is complete the mixture is stirred for 1 hour and the dichloromethane layer is separated. The aquesous layer is extracted with 100 mL of dichloromethane and the two organic phases are combined and washed with 20% NaHCO3 (aqueous), dried over anhydrous sodium sulfate and the solvent is distilled to yield a residue. The residue is tritrated with 1:1 ether:hexane and an off-white solid forms which is filtered, dried in vacuum at 60° C. for 4 hours. The reaction yields 1.2 g of product (69% yield) having a meting point of 141-142° C. 1H NMR (DMSO-d6 /50° C.) 10.1 (s, 1H), 9.92 (s, 1H), 8.48 (d, 1H, J=0.8), 8.10 (s, 1H), 8.08 (dd, 1H, J=8, J=8.8), 7.90 (d, 1H, J=8.8). 13C NMR (DMSO-d6 /50° C.) 191.8, 180.6, 158.1, 153.6, 132.9, 128.9, 127.5, 126.9, 118.8, 113.1.

Workup

  1. temperatureto reflux for 40 minutes
  2. temperatureThe reaction mixture is cooled
  3. customthe temperature below 25° C
  4. stirringis stirred for 1 hour
  5. customthe dichloromethane layer is separated
  6. extractionThe aquesous layer is extracted with 100 mL of dichloromethane
  7. washwashed with 20% NaHCO3 (aqueous)
  8. dry with materialdried over anhydrous sodium sulfate
  9. distillationthe solvent is distilled
  10. customto yield a residue
  11. filtrationhexane and an off-white solid forms which is filtered
  12. customdried in vacuum at 60° C. for 4 hours

Sources & evidence

ORD record
ord-9d95c912b7be4a139e0ac65079424647
Source dataset
uspto-grants-1999_08
Patent number
US05935982

Reaction notes

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