Tributyltin Chloride → HCID 86727238, compound

HRID 2173023Notes

Reaction equation

HRID 2173023 reaction equation
[S:1]1[C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[CH:3]=[CH:2]1.C([Li])CCC.[CH2:15]([Sn:19]([CH2:25][CH2:26][CH2:27][CH3:28])([CH2:21][CH2:22][CH2:23][CH3:24])Cl)[CH2:16][CH2:17][CH3:18].C(=O)(O)[O-].[Na+]>C1COCC1>[CH2:25]([Sn:19]([CH2:15][CH2:16][CH2:17][CH3:18])([CH2:21][CH2:22][CH2:23][CH3:24])[C:2]1[S:1][C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[CH:3]=1)[CH2:26][CH2:27][CH3:28]

Participants

6

Reactant 4

HCID 15096Tributyltin ChlorideHCID 289928Thieno(2,3-b)pyridineHCID 516892Sodium BicarbonateHCID 178418339Butyllithium

Product 1

HCID 86727238HCID 86727238, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a cold (−78° C.) solution of thieno[2,3-b]pyridine (2.000 g, 14.79 mmol) in anhydrous THF (50 mL) was added n-butyllithium (10.17 mL, 16.27 mmol) dropwise. The reaction mixture was stirred for 60 minutes at −78° C. A solution of tributylchlorostannane (4.79 mL, 17.75 mmol) in anhydrous THF (10 mL) was added and the reaction mixture was stirred for 30 minutes at −78° C. The solution was allowed to warm to room temperature over a period of 2 to 3 hours. Saturated aqueous sodium bicarbonate was added. The aqueous phase was extracted with ether (3×200 mL). The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and evaporated in vacuo. The crude product was purified by silica gel column chromatography, eluting with a gradient of 10-50% EtOAc and hexane over a period of 60 minutes. The desired fractions were collected and the solvent removed in vacuo to give the title compound (4.5 g, 72%) 1H NMR (500 MHz, DMSO-d6) δ ppm 0.87 (t, J=7.32 Hz, 9H), 1.13-1.20 (m, 6H), 1.32 (dq, J=14.64, 7.32 Hz, 6H), 1.52-1.64 (m, 6H), 7.34-7.42 (m, 1H), 7.51 (s, 1H), 8.25 (dd, J=7.81, 1.46 Hz, 1H), 8.50 (dd, J=4.39, 1.46 Hz, 1H).

Workup

  1. stirringthe reaction mixture was stirred for 30 minutes at −78° C
  2. temperatureto warm to room temperature over a period of 2 to 3 hours
  3. extractionThe aqueous phase was extracted with ether (3×200 mL)
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customThe crude product was purified by silica gel column chromatography
  8. washeluting with a gradient of 10-50% EtOAc and hexane over a period of 60 minutes
  9. customThe desired fractions were collected
  10. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-d18b48e954584755bfd2571d9dccd23b
Source dataset
uspto-grants-2015_06
Patent number
US09056873B2

Reaction notes

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