1,4-Dioxane → HCID 178503440, compound

HRID 2402445Notes

Reaction equation

HRID 2402445 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[C:10]([C:20]#[N:21])=[C:11](I)[S:12][C:13]=1[C:14]1[NH:18][CH:17]=[N:16][N:15]=1.[Cl-].[Li+].O1CCOCC1.CCCC[Sn]([C:43]1[CH:48]=[CH:47][N:46]=[C:45]([S:49][CH3:50])[N:44]=1)(CCCC)CCCC>[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[C:10]([C:20]#[N:21])=[C:11]([C:43]2[CH:48]=[CH:47][N:46]=[C:45]([S:49][CH3:50])[N:44]=2)[S:12][C:13]=1[C:14]1[NH:18][CH:17]=[N:16][N:15]=1

Participants

7

Reactant 4

HCID 312751,4-DioxaneHCID 433294Lithium ChlorideHCID 27632612-(Methylthio)-4-(tributylstannyl)pyrimidineHCID 178510278HCID 178510278, compound

Product 1

HCID 178503440HCID 178503440, compoundYield 47.3%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Procedure

4-(2,4-dichlorophenyl)-2-iodo-5-(4H-1,2,4-triazol-3-yl)thiophene-3-carbonitrile (0.140 g, 0.313 mmol), Lithium chloride (0.0398 g, 0.939 mmol), Copper(I) iodide (0.0179 g, 0.0939 mmol), and Tetrakis(triphenylphosphine)palladium(0) (0.0362 g, 0.0313 mmol) were combined in a 100 mL round-bottom flask under an atmosphere of Argon. 1,4-Dioxane (8.75 mL, 0.112 mol) was added followed by 4-tributylstannyl-2-thiomethylpyrimidine (0.194 g, 0.470 mmol). The solution was heated to reflux for 2 hours. The solvent was concentrated in vacuo and the residue was purified using ISCO chromatography on silica gel, elution 20% ethyl acetate in hexanes to ethyl acetate to afford the title compound (0.066 g, 47%). LCMS: (FA) ES+, 445, 447. 1H NMR (400 MHz, d1-chloroform) δ: 8.67 (d, J=5.21 Hz, 1H), 8.21 (s, 1H), 7.86 (d, J=5.20 Hz, 1H), 7.60-7.55 (m, 1H), 7.44-7.34 (m, 2H), 2.66 (s, 3H).

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 2 hours
  3. concentrationThe solvent was concentrated in vacuo
  4. customthe residue was purified
  5. washon silica gel, elution 20% ethyl acetate in hexanes to ethyl acetate

Sources & evidence

ORD record
ord-bbb39cce3e1b4eca9615e015f23468e3
Source dataset
uspto-grants-2014_08
Patent number
US08796314B2

Reaction notes

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