Diiodomethane → HCID 89924271, compound

HRID 1505678Notes

Reaction equation

HRID 1505678 reaction equation
[NH:1]1[CH:5]=[C:4]([C:6]2[CH:7]=[N:8][C:9]([C:12]3[CH:13]=[C:14](N)[CH:15]=[CH:16][CH:17]=3)=[N:10][CH:11]=2)[CH:3]=[N:2]1.[I:19]CI.N(OCCC(C)C)=O>O1CCOCC1.[Cu]I>[I:19][C:14]1[CH:13]=[C:12]([C:9]2[N:8]=[CH:7][C:6]([C:4]3[CH:3]=[N:2][NH:1][CH:5]=3)=[CH:11][N:10]=2)[CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 6346DiiodomethaneHCID 8053Isoamyl NitriteHCID 89924554HCID 89924554, compound

Product 1

HCID 89924271HCID 89924271, compoundYield 38%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a suspension of 3-[5-(1H-Pyrazol-4-yl)-pyrimidin-2-yl]-phenylamine (12.6 g; 53.2 mmol; 1.0 eq.) in Dioxane (500 mL) were added diiodomethane (21.6 mL; 266 mmol; 5.0 eq.), Copper(I) iodide (10.1 g; 53.2 mmol; 1.0 eq.) and isopentyl nitrite (21.5 mL; 159 mmol; 3.0 eq.). The reaction mixture was stirred at 100° C. for 2 hours and filtered. The filtrate was kept in a flask. The resulting green solid was suspended in dioxane (100 mL) and stirred at 100° C. for 30 minutes. The solid was then filtered off and the two filtrates were combined and concentrated under reduced pressure. The dark brown residue was sonicated in EtOAc (20 mL) and pentane (80 mL). The resulting brown solid was filtered, further washed with pentane and dried few hours under high vacuum to give the title compound as a brown solid (7.0 g; 38%). 1H NMR (300 MHz, DMSO-d6) δ 13.27 (brs, 1H), 9.20 (s, 2H), 8.71 (t, J=1.5 Hz, 1H), 8.52 (m, 1H), 8.39 (dt, J=8.0 Hz, 1.5 Hz, 1H), 8.21 (m, 1H), 7.89-7.86 (m, 1H), 7.35 (t, J=8.0 Hz, 1H). HPLC (Condition A): Rt 3.86 min (purity 67.6%). MS (ESI+): 349.3

Workup

  1. filtrationfiltered
  2. customThe filtrate was kept in a flask
  3. stirringstirred at 100° C. for 30 minutes
  4. filtrationThe solid was then filtered off
  5. concentrationconcentrated under reduced pressure
  6. customThe dark brown residue was sonicated in EtOAc (20 mL)
  7. filtrationThe resulting brown solid was filtered
  8. washfurther washed with pentane
  9. customdried few hours under high vacuum

Sources & evidence

ORD record
ord-e9e8d40e34dc4ed7950127b68b4191e4
Source dataset
uspto-grants-2015_12
Patent number
US09216991B2

Reaction notes

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