Acetic Acid → HCID 14204091, compound

HRID 1761700Notes

Reaction equation

HRID 1761700 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]2[CH:9]([C:10]#[N:11])[CH2:8][C:7]2=[CH:12][CH:13]=1)([O-])=O.C(O)C.C(O)(=O)C.[H][H]>[Pd].C(N(CC)CC)C.C(OCC)(=O)C.C1(C)C=CC=CC=1>[NH2:1][C:4]1[CH:5]=[C:6]2[CH:9]([C:10]#[N:11])[CH2:8][C:7]2=[CH:12][CH:13]=1

Participants

9

Reactant 4

HCID 176Acetic AcidHCID 702EthanolHCID 14794073HCID 14794073, compoundHCID 178418361HCID 178418361, compound2×

Product 1

HCID 14204091HCID 14204091, compoundYield 86.4%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 1140TolueneSolventHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

Into a 1-liter, three-necked flask equipped with a gas dipersion tube, reflux condenser, rubber septum and nitrogen inlet is placed 7 g (0.04 mole) of 5-nitro-1-cyanobenzocyclobutene and 400 ml of absolute 2B ethanol. The mixture is stirred under nitrogen and heat is applied to dissolve the solid. After adding 2.4 ml of glacial acetic acid and 1.6 g of 5 percent palladium on carbon, hydrogen flow is initiated and the mixture is hydrogenated at atmospheric pressure and ambient temperature. The hydrogenation is followed by thin-layer chromatography (silica gel; 70 percent toluene, 25 percent ethyl acetate, 5 percent triethylamine as eluent) and this shows the reaction is essentially complete in 1 hour. After 3 hours, the hydrogen flow is stopped and the system is purged with nitrogen for 15 minutes to remove excess hydrogen gas. The catalyst is removed by filtration using Celite and quickly quenched in water. The filtrate is evaporated to dryness on a rotary evaporator and the residue is treated with aqueous 10 percent sodium hydroxide. The aqueous solution is extracted with three 100-ml portions of ethyl ether, and the solutions are combined and washed once with 100 ml of water. The ethyl ether solution is dried over anhydrous potassium carbonate, filtered and evaporated on a rotary evaporator to give an amber-colored oil that solidified on standing. The product is pumped under vacuum overnight to remove the last traces of ethyl ether and stored under nitrogen. The infrared, 'H and 13C nuclear magnetic resonance are run. The yield is 86.4 percent.

Workup

  1. customInto a 1-liter, three-necked flask equipped with a gas dipersion tube
  2. temperaturereflux condenser
  3. temperatureheat
  4. dissolutionto dissolve the solid
  5. customis hydrogenated at atmospheric pressure and ambient temperature
  6. waitAfter 3 hours
  7. customthe system is purged with nitrogen for 15 minutes
  8. customto remove excess hydrogen gas
  9. customThe catalyst is removed by filtration
  10. customquickly quenched in water
  11. customThe filtrate is evaporated to dryness on a rotary evaporator
  12. additionthe residue is treated with aqueous 10 percent sodium hydroxide
  13. extractionThe aqueous solution is extracted with three 100-ml portions of ethyl ether
  14. washwashed once with 100 ml of water
  15. dry with materialThe ethyl ether solution is dried over anhydrous potassium carbonate
  16. filtrationfiltered
  17. customevaporated on a rotary evaporator
  18. customto give an amber-colored oil that
  19. customis pumped under vacuum overnight
  20. customto remove the last traces of ethyl ether

Sources & evidence

ORD record
ord-ee9e0dd1ce494c878f20cacf73016669
Source dataset
uspto-grants-1989_05
Patent number
US04826997

Reaction notes

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