Tributyltin Chloride → 5-(Tributylstannyl)-3-vinylisothiazole

HRID 2173014Notes

Reaction equation

HRID 2173014 reaction equation
[CH:1]([C:3]1[CH:7]=[CH:6][S:5][N:4]=1)=[CH2:2].C([Li])CCC.[CH2:13]([Sn:17]([CH2:23][CH2:24][CH2:25][CH3:26])([CH2:19][CH2:20][CH2:21][CH3:22])Cl)[CH2:14][CH2:15][CH3:16].C(=O)(O)[O-].[Na+]>C1COCC1>[CH2:23]([Sn:17]([CH2:13][CH2:14][CH2:15][CH3:16])([CH2:19][CH2:20][CH2:21][CH3:22])[C:6]1[S:5][N:4]=[C:3]([CH:1]=[CH2:2])[CH:7]=1)[CH2:24][CH2:25][CH3:26]

Participants

6

Reactant 4

HCID 15096Tributyltin ChlorideHCID 516892Sodium BicarbonateHCID 224916243-VinylisothiazoleHCID 178418339Butyllithium

Product 1

HCID 867272375-(Tributylstannyl)-3-vinylisothiazoleYield 44%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a cold (−78° C.) solution of 3-vinylisothiazole (300 mg, 2.70 mmol) in anhydrous THF (6.0 mL) was added n-butyllithium (1.855 mL, 2.97 mmol) dropwise. After stirring the reaction mixture for 60 minutes at −78° C., a solution of tributylchlorostannane (0.873 mL, 3.24 mmol) in anhydrous THF (1.5 mL) was added. The reaction mixture was stirred for 30 minutes at −78° C. and then allowed to warm to room temperature over a 1 hour period. Saturated aqueous sodium bicarbonate was added and the aqueous phase was extracted with EtOAc. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and evaporated in vacuo. The residue was purified by silica gel chromatography (Flash 60 column) eluting with hexane/EtOAc (19:1) to give the title compound as a pale yellow oil (472.8 mg, 44%). 1H NMR (500 MHz, CDCl3) δ ppm 0.90 (t, J=7.32 Hz, 9H), 1.13-1.18 (m, 6H), 1.34 (sextet, J=7.42 Hz, 6H), 1.52-1.61 (m, 6H), 5.50 (dd, J=11.23, 0.98 Hz, 1H), 6.00 (dd, J=17.60, 0.98 Hz, 1H), 6.96 (dd, J=17.57, 11.23 Hz, 1H), 7.33 (s, 1H).

Workup

  1. stirringThe reaction mixture was stirred for 30 minutes at −78° C.
  2. temperatureto warm to room temperature over a 1 hour period
  3. extractionthe aqueous phase was extracted with EtOAc
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customThe residue was purified by silica gel chromatography (Flash 60 column)
  8. washeluting with hexane/EtOAc (19:1)

Sources & evidence

ORD record
ord-80d90bdf952b48999d59d667b769add5
Source dataset
uspto-grants-2015_06
Patent number
US09056873B2

Reaction notes

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