Hydrochloric Acid → HCID 178428497, compound

HRID 1514190Notes

Reaction equation

HRID 1514190 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([C:9]#[N:10])[C:4]=1[CH3:11])#[N:2].Cl.[NH2:13][OH:14].C(N(CC)CC)C.Cl>C(Cl)(Cl)Cl.C1COCC1>[C:1]([C:3]1[C:4]([CH3:11])=[C:5]([C:9](=[NH:10])[NH:13][OH:14])[CH:6]=[CH:7][CH:8]=1)#[N:2]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8471Triethylamine2×HCID 443297Hydroxyamine hydrochlorideHCID 5883962,6-Dicyanotoluene

Product 1

HCID 178428497HCID 178428497, compoundYield 14.6%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

A suspension of 2,6-dicyanotoluene (25.0 g, 176 mmol), hydroxylamine hydrochloride (73.0 g, 1.06 mol) and triethylamine (142 g, 1.41 mol) in chloroform (500 ml) was stirred at 50° C. for 7 h, then allowed to stand at room temperature overnight. The reaction mixture was cooled in ice, treated with 5M HCl to pH1 and extracted three times with chloroform. The aqueous was extracted with THF (×7), cooled in ice, raised to pH4 with 40% NaOH and extracted with THF (×3). The latter THF extracts were combined and evaporated to dryness to give a buff solid consisting of the product and approximately a third of an equivalent of triethylamine (11.0 g). 1H NMR (400 MHz, d4-MeOH) δ (inter alia) 7.70-7.76 (1H, m), 7.57-7.63 (1H, m), 7.35-7.62 (1H, m), 2.58 (3H, s); MS (ES) C9H9N3O requires 175; found 176 [M+H]+. The former seven extracts of THF were combined, evaporated to dryness and dissolved in water. The aqueous solution was extracted twice with chloroform, adjusted to pH4 and extracted with THF (×3). Evaporation of the combined THF extracts gave a further 4.5 g of product.

Workup

  1. waitto stand at room temperature overnight
  2. temperatureThe reaction mixture was cooled in ice
  3. extractionextracted three times with chloroform
  4. extractionThe aqueous was extracted with THF (×7)
  5. temperaturecooled in ice
  6. temperatureraised to pH4 with 40% NaOH
  7. extractionextracted with THF (×3)
  8. customevaporated to dryness
  9. customto give a buff solid
  10. customevaporated to dryness
  11. dissolutiondissolved in water
  12. extractionThe aqueous solution was extracted twice with chloroform
  13. extractionextracted with THF (×3)
  14. customEvaporation of the combined THF

Sources & evidence

ORD record
ord-6f7bafb9369d409e95b645147a60a70b
Source dataset
uspto-grants-2012_07
Patent number
US08222245B2

Reaction notes

Loading…