Hexane → 2,6-Bis(tri-n-butylstannyl)-benzo[1,2-b:4,5-b']dithiophene

HRID 417723Notes

Reaction equation

HRID 417723 reaction equation
[S:1]1[CH:5]=[CH:4][C:3]2=[CH:6][C:7]3[S:8][CH:9]=[CH:10][C:11]=3[CH:12]=[C:2]12.[CH2:13]([Li])[CH2:14][CH2:15][CH3:16].[CH2:18]([Sn:22](Cl)([CH2:27][CH2:28][CH2:29][CH3:30])[CH2:23][CH2:24][CH2:25][CH3:26])[CH2:19][CH2:20][CH3:21].CC[CH2:34][CH2:35][CH2:36][CH3:37]>C1COCC1>[CH2:13]([Sn:22]([CH2:34][CH2:35][CH2:36][CH3:37])([CH2:18][CH2:19][CH2:20][CH3:21])[C:5]1[S:1][C:2]2=[CH:12][C:11]3[CH:10]=[C:9]([Sn:22]([CH2:27][CH2:28][CH2:29][CH3:30])([CH2:23][CH2:24][CH2:25][CH3:26])[CH2:18][CH2:19][CH2:20][CH3:21])[S:8][C:7]=3[CH:6]=[C:3]2[CH:4]=1)[CH2:14][CH2:15][CH3:16]

Participants

6

Reactant 4

HCID 8058HexaneHCID 15096Tributyltin ChlorideHCID 11106168Benzo[1,2-b:4,5-b']dithiopheneHCID 178418339Butyllithium

Product 1

HCID 585455822,6-Bis(tri-n-butylstannyl)-benzo[1,2-b:4,5-b']dithiopheneYield 42%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of benzo[1,2-b:4,5-b′]dithiophene (820 mg, 4.3 mmol) in THF (100 mL) under argon at −78° C. was added a solution of n-butyllithium (2.5 M, 3.44 mL, 8.6 mmol). The solution was stirred at −78° C. for 30 minutes and then warmed to −20° C. for 30 minutes. Tri-n-butyltin chloride (2.34 mL, 8.6 mmol) was added and the reaction mixture was stirred at −20° C. for 30 minutes and then allowed to warm to room temperature. After 16 hours, hexane was added and the reaction was successively washed with water and brine, dried (MgSO4), concentrated and purified by flash chromatography (100% hexanes). 2,6-bis(tri-n-butylstannyl)-benzo[1,2-b:4,5-b′]dithiophene (1.4 g, 42%) was isolated along with product contaminated with the monostannylated benzodithiophene. 1H-NMR: 400 MHz, (CDCl3) δ: 8.27 (s, 2H), 7.38 (s, 2H), 1.65-1.57 (m, 12H), 1.41-1.32 (m, 12H), 1.26-1.11 (m, 12H), 0.91 (t, J=7.3 Hz, 18H) ppm.

Workup

  1. temperaturewarmed to −20° C. for 30 minutes
  2. stirringthe reaction mixture was stirred at −20° C. for 30 minutes
  3. temperatureto warm to room temperature
  4. waitAfter 16 hours
  5. washthe reaction was successively washed with water and brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. custompurified by flash chromatography (100% hexanes)

Sources & evidence

ORD record
ord-1dacd07ca2f9470d9cedc4a4a85e3f8f
Source dataset
uspto-grants-2012_01
Patent number
US08088368B2

Reaction notes

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