Lithium Chloride → HCID 178509416, compound

HRID 2091697Notes

Reaction equation

HRID 2091697 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.C([Sn](CCCC)(CCCC)[C:27]1[CH2:28][CH2:29][O:30][CH2:31][CH:32]=1)CCC.[Cl-].[Li+]>O1CCOCC1.[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:27]2[CH2:32][CH2:31][O:30][CH2:29][CH:28]=2)[S:12][C:13]=1[C:14]1[NH:18][CH:17]=[N:16][N:15]=1

Participants

7

Reactant 3

HCID 433294Lithium ChlorideHCID 222522584-Tributylstannyl-3,6-dihydro-2H-pyranHCID 178510278HCID 178510278, compound

Product 1

HCID 178509416HCID 178509416, compoundYield 14.9%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 4-(2,4-dichlorophenyl)-2-iodo-5-(4H-1,2,4-triazol-3-yl)thiophene-3-carbonitrile (180 mg, 0.4 mmol), tributyl(3,6-dihydro-2H-pyran-4-yl)stannane (0.452 g, 1.2 mmol), lithium chloride (51.2 mg, 1.2 mmol), copper(I) iodide (7.6 mg, 0.04 mmol), tetrakis(triphenylphosphine)palladium (46.4 mg, 0.04 mmol) was dissolved in dioxane (20 mL) and heated to reflux for 3 hours under an atmosphere of argon. The solvent was removed 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 (24 mg, 14%). LCMS: (FA) ES+, 403. 1H NMR (400 MHz, d4-methanol) δ: 8.35 (s, 1H), 7.59 (d, 1H), 7.43-7.36 (m, 2H), 6.72 (dd, 1H), 4.38-4.36 (m, 2H), 3.97-3.94 (m, 2H), 2.71-2.68 (m, 2H).

Workup

  1. temperatureheated
  2. temperatureto reflux for 3 hours under an atmosphere of argon
  3. customThe solvent was removed
  4. customthe residue was purified
  5. washon silica gel, elution 20% ethyl acetate in hexanes to ethyl acetate

Sources & evidence

ORD record
ord-b0ba706119994a2a8d62e3b1cee26918
Source dataset
uspto-grants-2013_05
Patent number
US08440664B2

Reaction notes

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