Lithium Chloride → HCID 178452648, compound

HRID 2402444Notes

Reaction equation

HRID 2402444 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:22]([O:26][C:27](=[O:39])[NH:28][C:29]1[CH:34]=[C:33]([Sn](C)(C)C)[CH:32]=[CH:31][N:30]=1)([CH3:25])([CH3:24])[CH3:23].[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>[C:20]([C:10]1[C:9]([C:3]2[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=2[Cl:1])=[C:13]([C:14]2[NH:18][CH:17]=[N:16][N:15]=2)[S:12][C:11]=1[C:33]1[CH:32]=[CH:31][N:30]=[C:29]([NH:28][C:27](=[O:39])[O:26][C:22]([CH3:24])([CH3:23])[CH3:25])[CH:34]=1)#[N:21]

Participants

7

Reactant 3

HCID 433294Lithium ChlorideHCID 58095113HCID 58095113, compoundHCID 178510278HCID 178510278, compound

Product 1

HCID 178452648HCID 178452648, compoundYield 131.5%

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 (0.180 g, 0.0004 mol), tert-butyl[4-(trimethylstannyl)pyridin-2-yl]carbamate (0.285 g, 0.0008 mol), lithium chloride (0.051 g, 0.0012 mol), copper(I) iodide (0.023 g, 0.00012 mol), tetrakis(triphenylphosphine)palladium (0.046 g, 0.00004 mol) 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 (0.270 g, 40%). LCMS: (FA) ES+, 513, 515. 1H NMR (400 MHz, d4-methanol) δ: 8.39 (s, 1H), 8.38 (d, J=6.31 Hz, 1H), 8.23 (s, 1H), 7.55-7.50 (m, 1H), 7.47 (dd, J=5.28, 1.56 Hz, 1H), 7.39-7.35 (m, 2H), 1.54 (s, 9H).

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-ac2dbd74f2a5463b806722e8d2b420d5
Source dataset
uspto-grants-2014_08
Patent number
US08796314B2

Reaction notes

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