Tributyltin Chloride → HCID 21106087, compound

HRID 2235015Notes

Reaction equation

HRID 2235015 reaction equation
C([Li])CCC.[CH2:6]([S:8][C:9]1[N:13]2[C:14](C)=[CH:15][CH:16]=[CH:17][C:12]2=[CH:11][N:10]=1)[CH3:7].[CH2:19]([Sn:23](Cl)([CH2:28][CH2:29][CH2:30][CH3:31])[CH2:24][CH2:25][CH2:26][CH3:27])[CH2:20][CH2:21][CH3:22]>C1COCC1>[CH2:6]([S:8][C:9]1[N:13]2[C:14]([Sn:23]([CH2:24][CH2:25][CH2:26][CH3:27])([CH2:28][CH2:29][CH2:30][CH3:31])[CH2:19][CH2:20][CH2:21][CH3:22])=[CH:15][CH:16]=[CH:17][C:12]2=[CH:11][N:10]=1)[CH3:7]

Participants

5

Reactant 3

HCID 15096Tributyltin ChlorideHCID 12624793HCID 12624793, compoundHCID 178418339Butyllithium

Product 1

HCID 21106087HCID 21106087, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

n-Butyllithium (1.6 M, 4.2 mL, 6.7 mmol) is added slowly to a solution of the title B compound, 3-ethylsulfanyl-5-methyl-imidazo[1,5-a]pyridine (1.14 g, 6.4 mmol) in anhydrous THF (7 mL) at −78° C. The resulting solution is stirred at −78° C. for 1 h and tributyltinchloride (2.0 mL, 7.4 mmol) is added. The reaction is stirred at −78° C. for 1 h further, and then allowed slowly to warm to RT overnight. The reaction is quenched by addition of saturated aqueous ammonium chloride (15 mL) and the mixture is extracted two times with ethyl acetate. The organic extracts are combined, washed with aqueous potassium fluoride solution (3 M, 20 mL), dried over anhydrous magnesium sulfate, filtered and concentrated. The residue is purified by flash column chromatography on silica using 10% ethyl acetate in hexanes as the eluant to yield 3-ethylsulfanyl-5-tributylstannyl-imidazo[1,5-a]pyridine as a dark oil: 1H-NMR (CDCl3) δ 7.51 (s, 1H), 7.38 (dd, J=8.7, 1.2, 1H), 6.71 (dd, J=6.3, 1.5, 1H), 6.63 (dd, J=8.7, 6.3, 1H), 2.98 (q, J=7.4, 2H), 1.58-1.48 (m, 6H), 1.40-1.17 (m, 15H), 0.88 (t, J =7.5, 9H); 13C-NMR (CDCl3) δ 140.27, 133.53, 132.20, 124.88, 124.76, 124.63, 121.89, 118.77, 118.65, 118.56, 32.22, 29.66, 29.37, 29.30, 29.22, 27.94, 27.79, 27.68, 27.42, 15.59, 15.52, 14.83, 14.12, 14.03, 12.71, 12.65; MS (M+1)+ 465, 466, 467, 468, 469 (tin isotope pattern).

Workup

  1. stirringThe reaction is stirred at −78° C. for 1 h further
  2. temperatureto warm to RT overnight
  3. customThe reaction is quenched by addition of saturated aqueous ammonium chloride (15 mL)
  4. extractionthe mixture is extracted two times with ethyl acetate
  5. washwashed with aqueous potassium fluoride solution (3 M, 20 mL)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue is purified by flash column chromatography on silica using 10% ethyl acetate in hexanes as the eluant

Sources & evidence

ORD record
ord-2bb2a59e33d94b4ea29806fc5f1a37fc
Source dataset
uspto-grants-2010_05
Patent number
US07713991B2

Reaction notes

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