Hydrochloric Acid → HCID 12557197, compound

HRID 1781155Notes

Reaction equation

HRID 1781155 reaction equation
[C:1]([O-:4])([O-])=O.[Na+].[Na+].[C-]#N.[Na+].[Cu][C:11]#[N:12].Cl.[C:14]1([CH3:20])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>O.CCOC(C)=O>[CH3:20][C:14]1[CH:19]=[C:18]([CH:17]=[CH:16][C:15]=1[O:4][C:1]1[CH:18]=[CH:19][CH:14]=[CH:15][CH:16]=1)[C:11]#[N:12]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 1140Toluene2×HCID 8929Sodium CyanideHCID 10340Sodium CarbonateHCID 178418546HCID 178418546, compound

Product 1

HCID 12557197HCID 12557197, compoundYield 17%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
5 °C

Procedure

The amine prepared above (2.75 g, 13.8 mmol) was added to 2N HCl (20 mL), then cooled to 5° C., giving a thick purple slurry. A solution of sodium nitrite (0.84 g, 14.2 mmol) in water (2 mL) was added dropwise, keeping the reaction temperature -5° C. Addition of another small portion of sodium nitrite to the reaction resulted in a positive HONO test with a Kl-starch strip, so the pH was adjusted to 7-8 using solid Na2CO3. This solution was added in portions to a vigorously stirred mixture of toluene (10 mL) and a solution of sodium cyanide (1.65 g, 33.6 mmol) and copper(I) cyanide (1.45 g, 16.2 mmol) in water (15 mL), keeping the reaction temperature -5° C. The very thick, brown reaction mixture was diluted with more toluene, stirred at 5° C. for 15 minutes, then at room temperature for 2 hours. The reaction mixture was added to EtOAc and 2N HCl; the organic layer was dried with Na2SO4 and concentrated in vacuo. The residue obtained was chromatographed eluting with 95:5 hexane-Et2O to give the title compound as an orange-red oil (500 mg, 17%). 1H NMR (CDCl3) δ 7.55 (d, 1H), 7.40 (m, 3H), 7.20 (m, 1H), 7.00 (m, 2H), 6.79 (d, 1H), 2.35 (s, 3H). MS (DCl/NH3) m/e 227 (M+H+NH3)+.

Workup

  1. customthe reaction temperature -5° C
  2. waitat room temperature for 2 hours
  3. dry with materialthe organic layer was dried with Na2SO4
  4. concentrationconcentrated in vacuo
  5. customThe residue obtained
  6. customwas chromatographed
  7. washeluting with 95:5 hexane-Et2O

Sources & evidence

ORD record
ord-78415148fab842c09273602b43e2f3b1
Source dataset
uspto-grants-1997_05
Patent number
US05631401

Reaction notes

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