Tributyltin Chloride → HCID 71469915, compound

HRID 578735Notes

Reaction equation

HRID 578735 reaction equation
[CH2:1]([C:7]1[CH:11]=[CH:10][S:9][CH:8]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6].[Li][CH2:13][CH2:14][CH2:15][CH3:16].[CH2:17]([Sn:21](Cl)([CH2:26][CH2:27][CH2:28][CH3:29])[CH2:22][CH2:23][CH2:24][CH3:25])[CH2:18][CH2:19][CH3:20]>C1COCC1>[CH2:1]([C:7]1[CH:11]=[C:10]([Sn:21]([CH2:22][CH2:23][CH2:24][CH3:25])([CH2:17][CH2:18][CH2:19][CH3:20])[CH2:13][CH2:14][CH2:15][CH3:16])[S:9][C:8]=1[Sn:21]([CH2:26][CH2:27][CH2:28][CH3:29])([CH2:22][CH2:23][CH2:24][CH3:25])[CH2:17][CH2:18][CH2:19][CH3:20])[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6]

Participants

5

Reactant 3

HCID 15096Tributyltin ChlorideHCID 5668493-HexylthiopheneHCID 178418339Butyllithium

Product 1

HCID 71469915HCID 71469915, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-80 °C

Procedure

The dried THF (100 mL) is added with the 3-hexylthiophen (1 g, 5.94 mmol), cooled at −80° C., and slowly added with n-BuLi (5.94 mL, 14.85 mmol, 2.5 M in hexane) by one drop for 60 minutes. The reaction mixture is agitated at −80° C. for 3 hours. The reaction mixture is slowly added with tributyltin chloride (4.56 mL, 14.85 mmol) by one drop for 30 minutes. After the reaction mixture is agitated at −80° C. for 30 minutes, the reaction mixture rises to room temperature and is additionally agitated for 2 hours and is quenched with the NH4Cl aqueous solution. The reaction mixture is extracted with ethylacetate and then the organic layer is washed with water and dried with anhydrous sodium sulfate. The solvent was evaporated and the mixture before being purified was purified by the flash column chromatography using the silica gel quenched with triethylamine to obtain the desired compound 17 (4.21 g, 95% yield). 1H NMR (400 MHz, CDC13): δ=7.06 (s, 1H, CH—C-hexyl), 2.76-2.73 (t, J=12 Hz, 2H, ArCH2-, hexyl), 1.62 (m, 14H, ArCH2CH2-, hexyl+6×—(CH2)2-CH2-, butyl), 1.44-1.40 (m, 24H, 6×—(CH2)2-CH2-, butyl), 1.25-1.15 (m, 6H, CH3 (CH2)3-, hexyl), and 0.99-0.91 (m, 21H, CH3, hexyl+6×CH3, butyl) ppm. 13C NMR (100 MHz, CDC13): δ=144.30, 136.80, 136.05, 125.58, 31.64, 30.91, 29.25 29.09, 27.54, 27.37, 22.77, 14.12, 13.74, 10.78 ppm. C34H68SSn2 (746.39): calcd. C, 54.71; H, 9.18; S, 4.30; Sn, 31.81. found C, 54.59; H, 9.23; S, 4.40.

Workup

  1. stirringAfter the reaction mixture is agitated at −80° C. for 30 minutes
  2. customrises to room temperature
  3. stirringis additionally agitated for 2 hours
  4. customis quenched with the NH4Cl aqueous solution
  5. extractionThe reaction mixture is extracted with ethylacetate
  6. washthe organic layer is washed with water
  7. dry with materialdried with anhydrous sodium sulfate
  8. customThe solvent was evaporated
  9. customthe mixture before being purified
  10. customwas purified by the flash column chromatography
  11. customquenched with triethylamine

Sources & evidence

ORD record
ord-57dfc99df9fa4e9882633eefc40a7e82
Source dataset
uspto-grants-2015_05
Patent number
US09040655B2

Reaction notes

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